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 Nanostructured
Nonlinear Optical
Materials
Formation and Characterization

Rashid A. Ganeev
Optics and Spectroscopy Department,
Voronezh State University,
Voronezh, Russia
Elsevier
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Preface
The motivation in writing this book was related with the specific properties of small-
sized particles and structures and their nonlinear response in the field of strong laser
pulses, which became the area of interest from the very beginning of my career. The
topics presented in this book are mostly concerned with the nonlinear optical charac-
terization of various nanostructured media during my long-lasting collaboration with
numerous researchers and could not be realized without their generous efforts.
This book describes the analysis of the formation, characterization, and optical
nonlinearities of various nanostructures using different methods. The studies include
three groups of research fields. First group is related with the modification of the sur-
faces of materials for the formation of various nanostructures. Those studies include
the extended nanoripples formation using a few-cycle pulses, the analysis of the
nanoripples produced on the semiconductors possessing different bandgaps, and the
formation of nanopores, nanoholes, and nanowires using different conditions of laser-
matter interaction. Second group comprises the studies of ablated bulk and nanopar-
ticle targets, the low-order nonlinearities of metal and semiconductor nanoparticles,
and the nonlinear refraction and nonlinear absorption of c­ arbon-contained nanoparti-
cles. Finally, third group of studies is related with the high-order harmonic generation
in nanoparticle-contained plasmas.
These studies of the properties of nanostructured materials could not be realized with-
out the collaboration between various research groups involved in the studies of similar
topics. Among numerous colleagues I met and had the privilege to collaborate I would like
to thank H. Kuroda, M. Suzuki, T.Q. Jia, M. Baba (Saitama Medical U ­ niversity, Japan),
T. Ozaki, L.B. Elouga Bom (Institut National de la Recherche Scientifique, Canada), P.D.
Gupta, P.A. Naik, H. Singhal, J.A. Chakera, U. Chakravarty, M. Raghuramaiah, R.A.
Joshi, R.K. Bhat (Raja Ramanna Centre for Advanced Technology, India), J.P. Marangos,
J.W.G. Tisch, C. Hutchison, T. Witting, D.Y. Lei (­Imperial College, United Kingdom),
M. Castillejo, M. Oujja, M. Sanz, I. ­López-Quintás, M. Martín (Instituto de Química
Física Rocasolano, Spain), H. ­Zacharias, J. Zheng, M. Wöstmann, H. Witte (Westfäliche
Wilhelms-Universität, Germany), T. Usmanov, G.S. Boltaev, I.A. Kulagin, V.I. Redkore-
chev, V.V. Gorbushin, R.I. Tugushev, S.R. Kamalov (Institute of Ion, Plasma, and Laser
Technologies, Uzbekistan), O.V. Ovchinnikov (Voronezh State University, Russia), E.
Fiordilino, D. Cricchio, P.P. Corso (­Università degli Studi Palermo, Italy), M.K. Kodirov,
P.V. Redkin (Samarkand State University, Uzbekistan), A.L. Stepanov (Physics Tech-
nical Institute, Kazan, Russia), N.V. Kamanina (Vavilov State Optical Institute, Saint
Petersburg, Russia), and A.A. Ishchenko (Institute of Organic Chemistry, Kiev, Ukraine)
for their activity in the development of this interesting field of nanoscience.
Finally, as husband, father, and grandfather, I feel the privilege to underline the
role of my family in most of my endeavors.

Rashid A. Ganeev
Voronezh State University, Optics and Spectroscopy
Department, 1 University Square, Voronezh, Russia
 xiii

Introduction
B978-01243.6/ElsevirInc

The area of studies related with the small-sized objects is associated with the science
of nanotechnology, which commonly dubbed as nanoscience, and is an extremely de-
veloping field attracted the attention of enormous groups of researchers. It is hard to
imagine sizes of the book, which can describe all aspects of nanoscience. That is why
the researchers in their monographs dedicated to this area of studies try to restrict the
consideration of a few topics of the nanoscience. The frames of the reviews of previ-
ous studies overlap, from time to time, in these books, while providing a descriptive
character of the studies in the limited areas of interests of the authors. Present book
follows those principles and describes a few groups of studies, which for a long time
attracted the attention of this author. So we shortened the frames of consideration of
this extremely large field of nanoscience and tried to concentrate on some specific
topics, which did not previously find the attention from the point of view of nanopar-
ticles characterization.
As it was mentioned in preface, this book is dedicated to the analysis of the
formation, characterization, and, mainly, optical nonlinearities of various nanostruc-
tures using different methods. The discussed studies include three groups of research
fields. First group is related with the modification of the surfaces of materials for the
formation of various nanostructures including the extended nanoripples formation
using a few-cycle pulses, the analysis of the nanoripples produced on the semicon-
ductors possessing different bandgaps, and the formation of nanopores, nanoholes,
and nanowires using different conditions of laser-matter interaction. Second group
comprises the studies of ablated bulk and nanoparticle targets, the low-order non-
linearities of metal and semiconductor nanoparticles, and the nonlinear refraction
and nonlinear absorption of carbon-contained nanoparticles. Third group of stud-
ies is related with the high-order harmonic generation of ultrashort laser pulses in
nanoparticle-containing plasmas.
The formation of parallel fringes with characteristic spacing in the order of the
wavelength of the acting light (so-called “nanoripples”) is an interesting effect of
the interaction of ultrashort laser pulses with semiconductors and other materials. It
was primarily reported that the spacing between the fringes lay in the range of the
wavelength of the used femtosecond lasers, that is, it was about 800 nm or less for
most cases when Ti:sapphire lasers were employed. The interest in these periodic
surface structures was related to fundamental problems of interaction of ultrashort
pulses with different materials and to their possible practical applications. The ap-
pearance of these nanostructures was ascribed to the formation of diffraction gratings
with submicron spacing between the fringes; the interactions between laser light and
plasmon–polariton waves, which occur due to the initial heterogeneity of the surface,
the Bose condensation, and so on.

 xv

xvi Introduction

At the same time, the information about nanostructures with periods notably
smaller than the wavelength of the light (∼200 nm [1,2]) have aroused additional
interest connected, in particular, with the uncertain mechanism of the formation of
these structures. Several theoretical models have been proposed to explain the ap-
pearance of these short-periodic structures based on the principles used for interpret-
ing of nanostructures with long periods [3,4]. Note that a common feature of the
latter structures was approximate correspondence between the laser light wavelength
and the interfringe spacing. At the same time, the observed short-period structures,
which occur on semiconductor surfaces show not only much shorter distances be-
tween the fringes but also demonstrate some other specific features, among which are
the effects of the laser light polarization, bandgap width of the semiconductor, and
angle of incidence on the structural properties of short-period nanostructures. The
elucidation of the mechanisms of formation of short-period nanostructures requires
additional study because none of the mechanisms proposed thus far can explain, in
full measure, all characteristic features of this process.
Direct femtosecond laser surface nano- and micro-structuring is a versatile
method to tailor material surface morphologies, which enhance diverse interesting
physical properties. These include the ability to permanently modify the surface ab-
sorption spectrum or change appearing colors of metals and semiconductors without
any addition of pigments, the possibility to fabricate super-hydrophobic and self-
cleaning surfaces, and so on. In this context, the formation of laser-induced periodic
surface structures in the form of subwavelength ripples is extensively studied. By
carefully adjusting laser parameters like wavelength, polarization, pulse duration,
pulse number or pulse fluence, the shape, size, and orientation of the structures created
can be controlled, as shown by numerous empirical studies. Because this method of
structuring is an easy-to-implement, low-cost, top-down method, which is able to
fabricate periodic structures on the nanoscale without the sophisticated multistep pro-
cesses and ultrashort wavelengths needed for nanolithography, high spatial frequency
periodic structures has gained increasing attraction for practical applications.
Previous experimental studies have shown that the periodic nanostructure forma-
tion develops through the bonding structure change, the near-field ablation, and the
excitation of surface plasmon polaritons in the thin layer on the target surface. It has
also been demonstrated that use of multiple shots of low-fluence femtosecond pulses
is important for suppressing undesirable thermal processes in the nanostructures for-
mation through the ablation. The purpose of those studies was to analyze specific
features of the formation of nanostructures and short period nanostructures on the
surfaces of different semiconductors under variable experimental conditions. The
studies in this field include the analysis of different aspects of nanoripples formation
([5–12] to mention few of them).
In this book, we analyze the effect of the aforementioned and some other ex-
perimental parameters (light polarization, duration of the acting femtosecond pulses,
bandgap width of the semiconductor, angle of incidence of the laser beam upon the
surface, characteristics of the surrounding medium, and so on) on the pattern of the
nanostructure, including the cases when the regimes of formation of the long- and
  Introduction  xvii

short-period structures could be distinguished. We also show, in some cases, the for-
mation of nanoholes and nanodots on the surface of different semiconductors.
The third-order nonlinear optical susceptibilities of various media change in a
broad range. Nonlinearities responsible for variations in the refractive and absorb-
ing properties are especially important because they strongly affect the propagation
of intense radiation in media. Numerous investigations have been performed in this
field due to increasing interest in applications of nonlinear optical effects in opto-
electronics, various nonlinear optical devices, optical switching, and so on. Inter-
est in nonlinearities of different nanostructure media is also caused by their strong
nonlinear optical response attributed to the quantum size effect. The application of
nanostructures in the aforementioned fields and optical computers, storage devices,
nonlinear spectroscopy, and so on can lead to considerable developments of new
methods of the studies of matter. The studies in this field [13–15] were dedicated
to different aspects of applications and developments of new devices based on the
advanced nonlinear optical properties of nanoparticles.
In this book, we present the studies of the low-order nonlinear optical parameters
of different nanoparticles. Some of these nanostructured media are analyzed from the
point of view of their application as optical limiters of the laser radiation intensity.
The results of measurements of the nonlinear refractive indices, nonlinear absorption
coefficients, and third-order nonlinear susceptibilities of these media are presented
and discussed.
Coherent short-wavelength radiation is of increasing importance for a broad spec-
trum of basic and applied research in various fields of physical, chemical, and life
sciences. Among them, femtosecond time-resolved coherent diffractive imaging and
photo-induced processes on surfaces and nanoparticles, as well as lithography, plasma
diagnostics, and materials processing and diagnostics are of foremost interest. High-
order harmonic generation from femtosecond visible laser pulses allows producing
coherent radiation in the extreme ultraviolet spectral range. Table-top lasers render
these processes possible with the prospect of widespread scientific applications.
So far, however, only low conversion efficiencies for high-order harmonic
­generation have been obtained, despite the enormous efforts. Many interesting ex-
periments can be performed by harmonic generation based on laboratory scale fem-
tosecond lasers. These sources easily cover the spectral range between the 10- and
100-eV photon energy of the harmonics, and with few-cycle laser systems, even up
to several hundred eV. For practical applications of high-order harmonic sources,
higher conversion efficiency and, thus, an increase in the photon flux and the maxi-
mum photon energy of the harmonic radiation would be beneficial. High-order har-
monic generation itself can be used as a spectroscopic tool for analysis of the optical,
nonlinear optical, and structural properties of the harmonic generation emitters, pres-
ently comprising a few noble gases.
The generation of higher harmonics in laser-produced plasmas from various
solid-state targets, being for this purpose a relatively new and largely unexplored
medium, promises to yield these advances. Most interestingly, the studies have
shown that enhanced higher harmonics can also be generated from gas clusters
xviii Introduction

and ablated nanoparticles, which opens the door to applications of local field
enhancement­ [­16–22]. Thus, the above approach may be useful for producing an
efficient source of short-wavelength ultrashort pulses for various applications and
studies of the properties of harmonic emitters. Laser ablation-induced high-order
harmonic generation spectroscopy is a new method for materials science and can
be considered as one of the most important applications of harmonic generation.
In this book, we also discuss the realization of new ideas that have emerged over
the last few years, which led to further improved high-order harmonic generation
conversion efficiency through harmonic generation in specially prepared nanopar-
ticle-containing plasmas and allowed the spectral and structural studies of matter
through plasma harmonic spectroscopy. Nanoparticle research has demonstrated the
feasibility of increasing the efficiency of harmonic generation with the use of cluster
media. We note that the majority of previous works on harmonic generation involv-
ing nanoparticles was limited to the analysis of rather exotic clusters (Ar,Xe) that
were formed during rapid cooling resulting from the adiabatic expansion of gases
issuing from jet sources under high pressure.
The interest for nonlinear optical characterization of materials is closely related
to the new field of nanostructures formation during laser-matter interaction. The
formation of nanoripples, nanogrooves, nanoparticles, nanowires, and other exotic
nanostructures during laser ablation of different materials, formation of plasma
plumes containing clusters, characterization of their structural, morphological, opti-
cal, and nonlinear optical properties, use of nanostructures for various applications,
such as, for example, optical limiting and high-order harmonic generation, and many
other features of newly developed and commercially available nanoparticles open the
doors for their use in photonics, electronic industry, medicine and other scientific and
industrial applications.
The content of book shows that the advantages of nanomaterials for different
applications (in present case, nonlinear optical research) may further push this field
of morphology and high-order nonlinearities studies toward both fundamental and
practical needs thanks to better understanding of the processes involving in the laser-
nanostructure interactions. The formation of various nanostructures using different
methods is a broad field of studies, which shows specific methods, as well as advan-
tages and disadvantages of each approach. As main method of nanostructures forma-
tion in this book is, to some extent, a laser ablation, one can expect consideration of
other methods as well. Obviously, this book cannot be considered as a completed
­review of those methods, as some of them are too sophisticated and are out of the
scope of this book. Meanwhile, it can provide some bridge between the existing
methods of nanoparticles and nanostructures formation.
One can assume that single authorship can provide more homogeneity in the dif-
ferent topics and grant a better explanation from the basics. Being an author of this
book, I tried to combine different aspects of nanostructuring, nanoformation, charac-
terization, and application of small-sized species. These efforts obviously resulted in
broadening of the topics of this book. Combined by reasonable logic, various topics
can offer better overview and understanding of the main goals of this monograph.
  Introduction  xix

There are several books on nanomaterials. However, neither of them were dedi-
cated to their nonlinear properties and laser processing or laser characterization in
general. Often these publications are the multiauthor books that do not give enough
introductory information on the nonlinear optical properties of small sized species.
Indeed, there are not so much competitive books in this relatively new field. Most
of them combine different issues of nanomaterials studies. Meanwhile, the chapters
of those books are not closely related with each other. Obviously, different authors
are trying to underline some specific topics, which resulted in some incoherency in
presentation of a whole book. I, for myself, was an author of some chapters in such
books and can evaluate both drawbacks and advances in such sort of presentation.
The necessity in this book is related with the frequent requests of researchers
from different fields to the author to provide the information obtained during his nu-
merous studies of the nanomaterials. Currently, these studies are disseminated in dif-
ferent journals. The collection of these studies in a single book may help the reader to
learn about the interconnection of the morphological, optical, and nonlinear optical
features of these species.
The primary groups of the readers of this book comprise the researchers in the
fields of laser physics, nanomaterial studies, plasma physics, and nonlinear optics.
The book would be of interest for both academics and professionals in the applied
fields. Meantime, the book can be served as the source of information in different
fields of nanoscience for the high education students and postdocs, who are inter-
ested in further development of their career in the fields of laser-matter interaction,
coherent extreme ultraviolet sources, laser-produced plasmas, and nonlinear optics
of nanomaterials.
Obviously, it is an extreme task to combine in a single book the topics, which at-
tract different groups of readers. I tried to balance between pedagogical introductory
parts and more advanced topics so that the readership can include students as well as
more experienced researchers. The processing and characterization of nanomaterials
are certainly an important topic in the science of condensed matter. This book is not
only of interest to advanced students in physics, but also in chemistry and engineer-
ing. Thus the book can represent a reference textbook for advanced graduate courses.
The proposed field could be useful to Ph.D. students especially after one to two
years of experience. Based on my experience, as more advanced the paper (or book)
as more students will be interested in it. Obviously, it is not a text book. However,
the young people trying to advance in nanoscience have to make some efforts to
reach the level, which allows the reading of such sort of research studies. Conclud-
ing, though this book is mostly addressed to the experiences auditory, the PhD and
postdoc students can find many new and interesting information in this collection of
different topics of a specific field of nanoscience.
This book is organized as follows. To emphasize previous studies of periodic
structures, we discuss in Chapter 1 various methods of nanoripples formation on
the semiconductors possessing different bandgaps. In Chapter 2, the principles of
the formation of nanoparticles, nanopores, nanoholes, and nanowires using differ-
ent conditions of laser-matter interaction are analyzed. Chapter 3 is dedicated to
xx Introduction

the analysis of laser ablated bulk and nanoparticle targets and different modes of
nanostructured materials formation. The low-order nonlinear optical properties of
metal nanoparticles is discussed in Chapter 4. Chapter 5 considers nonlinear ab-
sorption and refraction in semiconductor and carbon-containing nanoparticles.
In Chapter 6, frequency conversion of ultrashort pulses in fullerenes is analyzed.
Chapter 7 is dedicated to the studies of the high-order harmonic generation in car-
bon-containing nanoparticles. Harmonic generation in metal and semiconductor
nanoparticles is discussed in Chapter 8. In Chapter 9 we analyze the peculiarities of
high-order harmonic generation in nanoparticles. Finally, we summarize the discus-
sion of the properties of nanostructured nonlinear optical materials.

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 CHAPTER

Periodic nanoripples
formation on the
semiconductors possessing
different bandgaps
1
1.1 NANORIPPLE FORMATION ON DIFFERENT BANDGAP
SEMICONDUCTOR SURFACES USING FEMTOSECOND PULSES
Surface structuring with lasers is a highly competitive method due to its capabil-
ity to implement changes in the structure design. Compared to the picosecond and
the nanosecond laser pulses, the energy in a femtosecond pulse can be precisely
and rapidly deposited in a solid material with fewer thermal effects. Therefore the
femtosecond lasers are widely used for microfabrication in transparent materials,
metals, and semiconductors for applications such as modifying the optical prop-
erties of the surface [1], improvement of photovoltaic devices [2] by increasing
their effective surface area, and in turn increasing the response and conversion effi-
ciency. The other applications include modification inside refractive index of bulk
materials for fabricating photonic devices, optical data storage, and biophotonic
components [3–5]. Mid-infrared femtosecond laser radiation is generally used for
the generation of surface ripples, also known as laser-induced periodic surface
structures (LIPSS).
Various mechanisms have been proposed to explain the nanoripple formation.
Initially, it was thought to be the result of the interference between the incident laser
light and the scattered light from the surface roughness [6]. However, if this mecha-
nism was to be true, nanoripple width should always be of the order of the incident
laser light wavelength, whereas, in many experiments, very narrow ripple formation
has been observed. For example, Ozkan et al. [7] found that ripples resulting from
248 nm femtosecond laser irradiation of thin diamond films had a period varying
between 50 and 100 nm. Yasumaru et al. [8] reported formation of ripple patterns
with mean periods of 100–125 and 30–40 nm on TiN and diamond-like carbon after
irradiation with 800 and 267 nm femtosecond pulses, respectively. To explain the
nanoripple formation in the case of metals, the surface plasmon created during initial
random surface heterogeneities was considered [9]. In dielectrics, the coupling of
the electron plasma wave and incident laser explains the observed periodic structure
in glass [10]. Other proposed mechanisms for ripple formation are self-organization
[11], Coulomb explosion [12], influence of second harmonic generation [13], aniso-
tropic local field enhancement invoking nanoplasmonics [14], etc.

Nanostructured Nonlinear Optical Materials. http://dx.doi.org/10.1016/B978-0-12-814303-2.00001-5 1

Copyright © 2018 Elsevier Inc. All rights reserved.
2 CHAPTER 1 Periodic nanoripples formation on the semiconductors

Below, we analyze surface nanoripple formation on different bandgap semicon-

ductors [15]. A study of the ripple formation with different laser parameters and
ambient media is presented with the objective of identifying conditions of forming
narrow period ripples. Nanoripples were formed using a Ti–sapphire laser with 8 mJ
energy, 45 fs pulse duration, and 800 nm wavelength (1.56 eV) at a fluence in the
range of 100 mJ cm−2–1 J cm−2. The effects of the number of laser shots, the angle
of incidence, polarization of the laser, fluence, incident laser wavelength (λ), band-
gap, and ambient medium were studied. Depending upon the experimental param-
eters, the nanoripple sizes varied in the range of λ/9–λ. Narrow nanoripples were
formed on the wide bandgap (WBG) semiconductors. The width of the nanoripples
decreased with the laser wavelength and the laser fluence. The observation of high
and low spatial frequency ripples in different conditions is explained considering the
transient metallic nature of the semiconductor surface on irradiation with intense
femtosecond pulses. The surface eventually supports the surface plasmon excita-
tion, which interferes with incident laser light for ripple formation. The very delicate
dependence of ripple period with incident laser parameters is attributed to the critical
role of electron density. The finding helps identifying suitable bandgap materials and
laser parameters for obtaining nanoripple period considerably small compared to the
incident laser wavelength.

1.1.1 EXPERIMENTAL ARRANGEMENTS AND RESULTS

For studying the nanoripple formation from ultrashort laser pulse irradiation of semi-
conductor materials of different bandgaps, the following semiconductor materials of
narrow (<1.5 eV, which is the energy of the incident 800 nm photon) bandgap mate-
rials such as InAs (0.36 eV), GaAs (1.42 eV), InP (1.35 eV), and wide (>1.5 eV)
bandgap materials such as GaP (2.3 eV), GaN (3.4 eV), SiC (3.37 eV), and ZnSe
(2.82 eV) were used. Multiple laser shots from a Ti–sapphire laser with 45 fs pulse
duration, and 800 nm wavelength were focused in air on the semiconductor wafers at
a fluence in the range of 100 mJ cm−2–1 J cm−2, that is, around the plasma formation
threshold. Using a beta barium borate (BBO) crystal, the second harmonic (400 nm)
of the 800 nm laser beam was also used to study the influence of the laser wavelength
on the ripple formation while keeping the other parameters the same.
Fig. 1.1 shows the surface morphologies resulting from the irradiation of a GaP
wafer by femtosecond pulses with two different polarizations and in two different
spatial regions. Fig. 1.1A shows the formation of spherical nanoparticles (∼100 nm)
with circularly polarized laser light also reported by several groups [16]. Fig. 1.1B
shows narrow nanoripples with ∼200 nm spacing at the peripheral regions of the laser
irradiated spot with linearly polarized laser pulses. Fig. 1.1C shows wider nanorip-
ples with about 600 nm spacing near the central hot region of the laser-irradiated
spot. As expected, for linearly polarized light, the nanoripple orientation was always
orthogonal to the laser polarization [17,18]. Nanoripple formation was observed with
10–100 shots fired on the semiconductors. It was also observed that number of shots
fired on the semiconductor did not have any effect on the ripple period.
 1.1 Nanoripple formation 3

FIGURE 1.1 GaP Irradiated by 800 nm Ultrashort Laser Pulses,

(A) with circularly polarized beam, and (B) and (C) with linearly polarized beam in two
different regions; (B) is around the periphery of the irradiated spot (low fluence); and (C)
is in the central region (high fluence). [The length of the horizontal bar is 1 µm in (A), (B),
and 2 µm in (C).].
Reproduced with permission from U. Chakravarty, R.A. Ganeev, P.A. Naik, J.A. Chakera, M. Babu, P.D. Gupta,
Nanoripple formation on different band-gap semiconductor surfaces using femtosecond pulses, J. Appl. Phys.
109 (8) (2011) 084347, AIP Publishing.

Fig. 1.2 shows the nanoripple formation using linearly polarized laser pulses. In
the narrow bandgap semiconductors such as GaAs and InP, the scanning electron
microscope (SEM) pictures of the irradiated spot show the spacing to be of the order
of 500–600 nm. On the contrary, in WBG materials such as GaN and SiC, the spac-
ing is of the order of 170–270 nm. Thus it was observed that, in general, the narrow
nanoripples are formed from material with a WBG. This observation of narrow ripple
formation in WBG semiconductor is consistent with previous reported results by
Borowiec et al. [19], but no explanation of the physical processes involved was given
in those experiments.
Fig. 1.3 shows different microstructure formations using different fluences and
ambient conditions for narrow bandgap semiconductors such as GaAs. The SEM pic-
ture of the irradiated spot, as seen in Fig. 1.3A, shows that, at a high fluence in air, no
nanoripple formation takes place, and only random heterogeneities of a few microns
order appear. Fig. 1.3B shows formation of nanoripples of a typical size of 600 nm
at low fluence (in air). Interestingly, Fig. 1.3C shows formation of nanoholes at high
fluence in water. Fig. 1.3D shows narrow nanoripples of 150 nm size in GaAs at low
fluence in water. This shows the crucial role of the ambient medium in formation of
the nanoripples. Very narrow nanoripples were observed in narrow bandgap materi-
als such as GaAs in water, whereas in air, the corresponding nanoripple period was
of the order of the laser wavelength. Even for a WBG material such as GaP, which
4 CHAPTER 1 Periodic nanoripples formation on the semiconductors

FIGURE 1.2 Nanoripple Formation Using 800 nm Pulses in Narrow Bandgap Semiconductors:
(A) GaAs and (B) InP; and in wide bandgap semiconductors: (C) GaN and (D) SiC [The
length of the horizontal bar is 1 µm in (A), (B), (C), and (D).].
Reproduced with permission from U. Chakravarty, R.A. Ganeev, P.A. Naik, J.A. Chakera, M. Babu, P.D. Gupta,
Nanoripple formation on different band-gap semiconductor surfaces using femtosecond pulses, J. Appl. Phys.
109 (8) (2011) 084347, AIP Publishing.

FIGURE 1.3 Nanoripple Formation Using 800 nm Pulses in GaAs:

(A) at high fluence in air, (B) at low fluence in air, (C) at high fluence in water, and (D) at
low fluence in water. [The lengths of the horizontal bars correspond to 5 µm in (A), (B),
and (C), and 1 µm in (D).].
Reproduced with permission from U. Chakravarty, R.A. Ganeev, P.A. Naik, J.A. Chakera, M. Babu, P.D. Gupta,
Nanoripple formation on different band-gap semiconductor surfaces using femtosecond pulses, J. Appl. Phys.
109 (8) (2011) 084347, AIP Publishing.
 1.1 Nanoripple formation 5

shows narrow nanoripples of period ∼200 nm in air, a narrower period of 150 nm

was observed during irradiation in water.
Fig. 1.4 shows the angular dependence of nanostructure size obtained from nar-
row (GaAs) and wide (GaP) bandgap materials irradiated by 800 nm pulses in water.
It was observed that, for the narrow bandgap (GaAs) semiconductor, the ripple size
increased with increasing angle of incidence, as shown in Fig. 1.4A. In the case of
the WBG (GaP) material with increasing angle of incidence, the ripple period first
increases and becomes constant at higher angles, as shown in Fig. 1.4B. It was men-
tioned earlier in the context of Fig. 1.3C that, at high fluence, nanoholes are formed
in GaAs. Fig. 1.4C shows that the size of the holes increases with increasing the
angle of incidence of the incident p-polarized light. In many photonic applications,
for example, two-dimensional photonic crystals and micro-diffraction elements, the
nano/micro holes on the surface of bulk materials are required as the building blocks.
Although the mechanism of formation of such structures is still not clear, this process
was achieved during irradiation in water medium, thus emphasizing the role of dense
surrounding medium in formation of such novel hole structures.
It is commonly accepted that the nanoripple width is dependent on the wave-
length of the incident light. Therefore to obtain narrow nanoripples, second harmonic
of the fundamental laser radiation is a better choice. Fig. 1.5 shows the influence of
laser wavelength on nanoripple formation. Fig. 1.5A and B show that, in the case of
SiC, the use of 400 nm wavelength reduces the ripple period by more than a factor of
two as compared to the nanoripples produced by the 800 nm pulses (from 190 nm to
about 90 nm). Similarly, for a narrow bandgap material such as InP, there is a reduc-
tion of ripple period from 620 nm to about 280 nm, as shown in Fig. 1.5C and D. It
may be noted that, for GaP, the ripple period using 400 nm pulse becomes larger than
that formed using 800 nm pulses (from 180 nm to about 300 nm).

1.1.2 DISCUSSION OF EXPERIMENTAL RESULTS AND DESCRIPTION

OF THE MODEL
The consistent observations regarding the nanoripple formation are as follows: (1)
the ripple period is larger at higher fluence, (2) the ripple period is large for the mate-
rials having bandgap narrower than the incident photon energy compared to that for
materials having a wider bandgap, and (3) a denser ambient medium results in the
formation of narrower ripple period. The plausible explanation for such observations
is consistent with the theory that ripple formation is due to excitation of the surface
plasmon at the semiconductor surface by the incident laser light with the rough tar-
get surface. The surface plasmon is a well-known phenomenon in the context of the
metals, which have free electrons for excitation of this longitudinal charge density
oscillation. However, in the case of semiconductors, the origin of free electrons is
because of the excitation of free electrons due to multiphoton ionization by the laser.
The typical intensity of 2 × 1012 W cm−2 is just sufficient to start plasma formation
for an ultrashort (45 fs) laser pulse, wherein multiphoton ionization is the dominant
process. These laser-generated free electrons give a transient metallic character to
6 CHAPTER 1 Periodic nanoripples formation on the semiconductors

FIGURE 1.4 Angular Dependences of Formation of Various Nanostructures Using 800 nm

Pulses in Water.
(A) Nanoripple formation in GaAs, (B) Nanoripple formation in GaP, and (C) Nanohole
formation in GaAs.
Reproduced with permission from U. Chakravarty, R.A. Ganeev, P.A. Naik, J.A. Chakera, M. Babu, P.D. Gupta,
Nanoripple formation on different band-gap semiconductor surfaces using femtosecond pulses, J. Appl. Phys.
109 (8) (2011) 084347, AIP Publishing.
 1.1 Nanoripple formation 7

FIGURE 1.5 Nanoripple Formation Using 800 nm Pulses and 400 nm Pulses Respectively in
Wide Bandgap Semiconductors:
SiC (A) and (B), GaP (E) and (F), and in narrow bandgap semiconductor InP (C) and (D).
[The length of the horizontal bar is 2 µ m in (A), 500 nm in (B), 5 µ m in (C), 1 µm in (D),
1 µm in (E), and 2 µm in (F).].
Reproduced with permission from U. Chakravarty, R.A. Ganeev, P.A. Naik, J.A. Chakera, M. Babu, P.D. Gupta,
Nanoripple formation on different band-gap semiconductor surfaces using femtosecond pulses, J. Appl. Phys.
109 (8) (2011) 084347, AIP Publishing.

the molten surface, which can now support the surface plasmon. During the initial
few shots, the surface roughness is enhanced due to irradiation by the high-intensity
pulses and formation of random nanostructures. The subsequent shots fired on the
roughened surface lead to more efficient excitation of surface plasmon. The molten
material assumes the shape of a grating, which satisfies the relation between wave
vectors of the incident laser (which depends on its wavelength, the angle of inci-
dence, and the refractive index of the ambient medium) and the surface plasmon
(which depends on the electron density of the molten surface). This grating gets
frozen once the material cools down as soon as the laser pulse ends giving rise to the
observed nanoripples. The wave vector of this grating satisfies the following relation,
as per the momentum conservation [18]
G = k i − ks , (1.1)
8 CHAPTER 1 Periodic nanoripples formation on the semiconductors

where ki is the wave vector of incident laser and ks is the wave vector of surface
plasmon. By substituting the expression for k's in terms of corresponding wave-
lengths, and |G| as 2π/d (where d is the ripple period), one gets the expression for
d as [18]
λL
d= (1.2)
λL
± µ sin θ
λS
Here λL, λS, θ, and µ are the incident laser wavelength (in vacuum), the sur-
face plasmon wavelength, the incident angle, and the refractive index of the ambient
medium, respectively. It is clear from Eq. (1.2) that for normal incidence (i.e., θ = 0)
d = λS. Thus at normal incidence the ripple period d is equal to the surface plasmon
wavelength, which is obtained from its dispersion relation as
λL
λS = (1.3)
εε m
ε + εm
Here ε is dielectric constant of the surface plasma created by the intense femto-
second pulse, and εm is the dielectric constant of the ambient medium (i.e., εm = µ2;
1 for air and 1.76 for water).
Because the multiphoton ionized surface has free electrons, its dielectric constant
can be taken similar to a plasma, that is, (neglecting the collision term frequency)
ne
ε = 1− (1.4)
nc

where ne is the surface plasma free electron density, and nc is the critical density cor-
responding to the laser wavelength. Putting the expression of ε in Eq. (1.3) and then
using Eq. (1.2), one gets for the case of normal incidence
λL
d= (1.5)
(
ε m 1−
ne
nc )
ε m + 1− ( ne
nc )
From Eq. (1.5), it is clearly seen that the ripple period is related to the incident
laser wavelength, electron density of the surface plasma, and the dielectric constant
of the ambient medium. It is also evident from the expression that real values of d
will be obtained only if
ne < nc or ne > ( ε m + 1) nc (1.6)

When this condition given by Eq. (1.6) is not satisfied, the nanoripples are not
formed. Fig. 1.6A shows the variation of nanoripple period in air and water with
electron density plotted using Eq. (1.5) for 800 nm wavelength. Fig. 1.6B shows the
same curve for 400 nm wavelength.
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 VI.

On the 17th of the following March, at the Hôtel de Chimay, now

connected with the École des Beaux Arts, the exhibition of the works
of him whom we have surnamed the “Primitif” was opened. All the
works of Bastien, with the exception of the Jeanne d’Arc, were
collected there.
On visiting this exhibition the most prejudiced minds were struck
with the suppleness, the fecundity, and power of the talent of this
painter, carried off at the age of thirty-six. For the first time his varied
and original work could be judged as a whole.
One could study in detail these productions of a thoroughly
conscientious artist, and follow the growth of each composition as
one follows the development of a beautiful plant—first in the
drawings, so pure, so sober, and expressive; then in the sketches so
truthful and sincere; and, lastly, in the finished pictures, so
harmonious and luminous. By the side of the great pictures, Les
Foins (The Hay), La Saison d’Octobre (October), Le Mendiant (The
Beggar), Père Jacques (Father Jacques), and L’Amour au Village
(Love in the Village), like windows opening upon life itself, one
admired that collection of small portraits in which the most
penetrating physiological observation was united with an execution
most masterly, precise, and delicate. One passed delighted from
those interiors worthy of the Dutch painters, such as La Forge and
La Lessive, to the landscapes breathing the odours of the fields and
of the woods, such as Le Vieux Gueux (The Old Beggar), Les
Vendanges (The Vintage), La Prairie (The Meadow), La Mare (The
Pool), Les Blés Mûrs (Ripe Corn), or to those full of air and motion,
like London Bridge and the Thames; then one stopped before La
Petite fille allant à la École (The Little Girl going to School), or that
poetic Idyl, Le Soir au Village (Evening in the Village).
 The Inn.
By Jules Bastien-Lepage.
In this exhibition containing more than two hundred canvases and
a hundred drawings, there was nothing trifling, nothing indifferent.
The smallest sketches were interesting because they revealed
passionate worship of what is simple and natural, hatred of the
almost and the conventional, and the incessant striving of the artist
after his ideal, which is Truth.
A healthy and robust poetry exhaled from this collection. One left
the Hôtel de Chimay with a sensation of strengthening and reviving
pleasure, such as one gets from certain aspects of nature—deep
woods, limpid waters, and the bright sky of a summer morning.
 Unhappily this joy was mixed with the sad thought of the sudden
death of the young man who had produced all this masterly work.
On first entering these rooms reserved for his pictures I was, for a
long time, impressed with a feeling that I had already experienced at
the exhibition of the works of the talented young artist, Mdlle.
Bashkirtseff, mown down like Bastien, in full youth, and at the same
time as he. This cruel death seemed only a bad dream.
On seeing again these unfinished sketches, these perfect
portraits, these canvases that I had seen him paint one after another,
I felt as if I was conversing with the painter and the friend who had
created all this. I felt that he was still living and in possession of all
his force. I expected every moment to see him appear among us,
smiling, happy, fortified by the now unanimous admiration of the
crowd gathered before his work.
Alas! instead of himself my eyes only met his portrait, placed in
the first room, and the mournful eloquence of the wreaths and
flowers attached to the frame recalled me harshly to the heartrending
reality.
The poor “Primitif” will paint no more. The atelier at Damvillers
where we have spent such happy hours is closed for ever. The
peasants of the village will no more meet their countryman on the
roads where he used to work in the open air. The rustic flowers that
he used to paint in the foreground of his pictures, the blue chicory
and the groundsel, will flower again this summer by the edges of the
fields, but he will not be there to study and admire them.
Among the sketches exhibited by the side of the great pictures
there was one that I had already remarked at Damvillers, and that I
now saw again with deep emotion. It represents an old peasant
woman going in the early morning into her garden to visit her apple
tree in blossom. The nights of April are perfidious, and the spring
frosts give mortal wounds; the old woman draws to her a flowering
branch and inspects with anxious eye the disasters caused by the
hurtful rays of the red moon. Bastien-Lepage was like this tree, full of
sap and of promising blossom. For years the heavens had been
clement to him, and the flowers had given many and rich fruits; then
in a single night a murderous frost destroyed all—the open flowers
by thousands, and the tree itself. All that remains is the splendid fruit
of past seasons, but the exquisite flavour of that the world will long
enjoy.
Things truly beautiful have wonderful vitality and last on through
the centuries, hovering above the earth where the generations of
men go turn by turn to sleep,—and this survival of the works of the
spirit of man is perhaps the surest immortality upon which he can
count.
JULES BASTIEN-LEPAGE AS
ARTIST.
Bas-Relief Portrait of Bastien-Lepage.
By Augustus Saint-Gaudens.
 JULES BASTIEN-LEPAGE AS ARTIST.

The work of Bastien-Lepage ranks, to my mind, with the very best in

modern art. He brought to us what was in some ways a new view of
nature—one whose truth was at once admitted, but which was
nevertheless the cause of much discussion and criticism. It was
objected to mainly, I think, as not being in accord with established
rules, but nevertheless the objectors expressed their admiration for
the skill of the painter; while, on the other hand, for those who
accepted him (chiefly the younger men these), no praise was too
great, no admiration too enthusiastic.
It is only a few years since his untimely death was mourned as a
loss to the whole art-world, for his whole career is so recent that his
fellow-students are still young men, many of them only now
beginning to obtain full recognition; and yet it is perhaps long enough
ago to enable his work to be considered as a whole, and his place in
the art-movement to be seen. For although he was an innovator, and
one showing in all he did a strong individuality, the general direction
of his genius was given him by the artistic tendencies of his time.
It will be generally admitted that if painting has made any advance
in our day, if it shows in any direction a new departure, or fresh
revelation of the beauty that exists throughout nature, it is in the
development of the problems which have arisen from the study of
landscape and of the effects of light. There now prevails a close and
sincere study of nature, founded on the acceptance of things as they
are, and an increasing consciousness on the part of artists (or
perhaps it would be more correct to say an increasing courage on
the part of artists to express their conviction) that a picture should be
the record of something seen, of some impression felt, rather than
be formally constructed. And men have awakened at length to see
that all nature is beautiful, that all light is beautiful, and that there is
colour everywhere; that the endeavour to realize truly the natural
relation of people to their surroundings is better than to follow
unquestioning on the old conventional lines. This is, roughly
speaking, the modern standpoint, and it cannot be denied that it is
an enormous advance on the accepted artistic ideals of thirty or forty
years ago. And to the men who have brought this about—to the Pre-
Raphaelite brotherhood; to Millet, Corot, Rousseau, Courbet, Manet,
and Mr. Whistler—to all those who have fought the battle and to
whom our present clearer outlook is due, we owe a lasting debt of
gratitude.
It is a little surprising now, that the work of Bastien-Lepage, based
as it is on the simple acceptance of nature, should have caused so
much discussion on its first appearance. For time has justified him;
we feel on comparing his work with other men of his time that it
marks a new departure, and we realize that it has helped to form our
present standpoint. But as the majority of people tune their eyes by
pictures and not by nature, and only admire in nature that which is
made manifest to them by their artistic prophet, it may be taken as a
compliment to a man of independent genius that when he discloses
a fresh view of nature, it is not for some time accepted. “Good
gracious, sir!” said an eminent critic, referring to Claude Monet, “like
nature? Yes; of course it’s like nature; but a man has no business to
choose that aspect of it!”
Every picture may be said to appeal to the spectator from two
sides or points of view—the literary and the æsthetic.
A picture may tell its story to perfection—may point a moral and
all the rest of it, and so fulfil the purpose of its author—and still, or,
as some extreme persons would say, therefore—may be bad art,
may indeed be not worthy to rank as art at all. Such pictures are
frequently seen. And again, a picture may, by raising and defining to
some inner sense emotions dimly felt by us before nature, leave us
with a fuller sense of beauty, a feeling of something revealed to us.
And yet it need have no subject or story. We are convinced that this
picture is beautiful: that no other form of artistic expression can
precisely so touch us. Such pictures are rare, but happily they do
exist. Yet, from the nature of things, it is impossible but that such a
picture should speak to some—ever so slight—extent to the mind;
and also the most literary picture is never without evidence of some
desire to please the eye.
The work of Bastien-Lepage seems to me to embrace both these
points of view. The literary and æsthetic sides of art were very evenly
balanced in him. If we take any individual work, as, for example, the
Beggar, we find a most perfect realization of character: the whole
life-history of the man seen and brought before us—evidently this
was the motive of the picture; yet the painting is in itself so full of
charm, the perception of colour so fine, that we feel he was equally
interested in that. He tried to hold the balance even. His work shows
an extraordinary receptive power, an unequalled (almost microscopic
on occasion) clearness of vision, allied with an absolute mastery of
his material. His attitude towards nature is one of studied impartiality,
and seems to show the resolute striving of an intensely sympathetic
nature to get at the actual optical appearances and to suppress any
hint of his own feelings. And his subjects are presented with such
force and skill that their truth to nature is at once felt, and if a painter,
you cannot fail also to feel the charm of his simple and sincere
method. You cannot tally it by any other painter’s work: it stands by
itself.
His impartial attitude towards his model constitutes one of
Bastien-Lepage’s distinctions. I am not sure that it is not the distinct
note of all his work. He paints a man—and the man stands before
you, and you ask yourself, “What is he going to say? What does the
artist wish to express?” You may make what you can of him; Lepage
gives you no clue. To me, I confess, this quality is a very high one; it
seems to indicate a great gift, and to be, if I may presume to say so,
akin to Shakespeare’s method of presenting his characters without a
hint of his own feelings towards them.
Although it is no doubt owing to Millet that Lepage’s eyes were
opened to the paintableness of country life, he saw his subjects in
his own way and approached them from his own point of view. With
Millet the subject and type were everything—the individual nothing.
He was passionately moved by his subject, and once its action and
sentiment were expressed, everything was subordinated to them. He
cared nothing for the smaller truths of detail provided the general
impression were true to his mental image, and his aim was avowedly
to impose his mental impression on the spectator. Lepage, on the
contrary, appears to avoid communicating his mental impression. He
will give you the visual impression, as truly as he possibly can; you
may, if you please, find—as he has found—pathos and poetry in it:
as before the same scene in nature, if you have sympathy; but for
his part he will not help you by any comment of his own.
And whereas with Millet the interest always centres in the subject,
in Lepage it centres in the individual. His pictures become portraits.
He chooses a good type, and sets himself to paint him at his work
and amid his natural surroundings, and, somehow or other, the
subject, as motive and reason for the picture, takes a subordinate
place. And yet this is not because anything belonging to the subject
is slurred, but because the attention is taken beyond the subject to
the actors in it. For his figures not only live; they convince us of their
identity as individuals, and gradually we get so interested in them
that we begin to forget what they are doing, and almost to wonder
why they are there. We are, in fact, brought so close to them that we
cannot get away from the sense of their presence. It is no small
tribute to Lepage’s skill that his people do so interest us; but is not
this interest a conflicting element in the picture? Is it to the
advantage of the picture that the interest should be so equally
divided? I cannot tell: when before a picture of Lepage’s I accept it in
everything—on thinking it over, I begin to doubt. There is no room for
doubt about Millet; no mistake about what he meant. With him the
attention is always concentrated on the business in hand: and
without desiring to qualify the great respect and admiration which I
have for Lepage’s work, it seems to me that the point of view of
Millet included more essential truths (or perhaps excluded those
which were not essential to the expression of the subject); and that
for this reason Lepage’s most successful pictures depend least upon
the interest of subject, and most upon the interest of portraiture.
For it is in his portraits that the great capacity of the man is best
seen; and they are altogether admirable. His people stand before
you, and you feel that they must be true to the very life. He loves to
place them in an even, open, light, and simply accepting the ordinary
conditions of his sitters, produces a surprisingly original result. There
is no forcing of effect, no slurring of detail—everything is searched
out relentlessly, lovingly. There is the same impartial standpoint—the
same apparent determination to keep himself out of the picture.
From the artist’s point of view they are altogether delightful; modelled
with the thoroughness of a sculptor, the colour and atmosphere are
always true, and the execution is unlaboured and direct. It would be
difficult to point to any modern portraits which surpass for technical
mastery and charm such works as the “First Communion,” the
portraits of his parents, his grandfather, of M. Theuriet, Albert Woolf,
Sarah Bernhardt, “Pas Meche,” and the Beggar. Each of these is a
complete picture, as well as being a portrait. The elaborate dress of
the actress, the cheap muslin and ill-fitting gloves of the child, in the
“First Communion”—all the matters of minor detail are dwelt on with,
in each case, the fullest sense of their literary importance to the
picture, and yet the painting of these things, as of all else, is so
delightful in itself that the artist desires no other reason.
While landscape entered as a matter of course into his rustic
pictures, it was always subordinate to the figures; although he
carried the finish of the foregrounds in these pictures to the farthest
possible point, delighting to express the beauty of everything—
weeds, sticks, stones, the clods of earth—all was felt, and shown to
be beautiful. But he painted also some admirable landscapes: of
these I have seen but few, and the recollection of one in particular
remains with me as one of the most beautiful things I have seen. It is
a field of ripe golden corn; beyond are the distant fields and low hills,
and overhead in the clear blue sky a few clouds. The corn is swaying
and rustling in the breeze, and small birds are flitting about. The
whole scene is bathed in daylight and fresh air: with no great stretch
of fancy one can see the corn moving, and hear the singing of the
birds. One is filled with a sense of the sweetness of nature and the
beauty of the open fields. And the picture is so simple—no effort in
design, no artifice apparent—it impresses as a pure piece of nature.
This love of nature and resolute determination not to depart from
the strict literal truth as he saw it, marks all the work of Bastien-
Lepage. As far as it was possible for an artist nowadays, he appears
to have been uninfluenced by the old masters. The only lesson he
seems to have learnt from them was that nature, which sufficed for
them, should suffice for him also. It is this attitude of mind which
brings him into kinship with the early painters, and which led to his
being styled “the primitive.” He did not set out to form his art on the
methods of the older painters, but going as they did, direct to nature,
he resolutely put on one side (as far as was possible to one familiar
with them) the accepted pictorial artifices. He seems to have set
himself the task of going over the ground from the beginning; and the
fact that his uncompromising and unconventional presentment of his
subjects should be expressed by means of a most highly
accomplished, very modern, and very elegant technique, was one of
the things which, while it greatly charmed, at the same time puzzled
and surprised people. It was so different from what had been seen,
or might reasonably have been expected; and one can understand
some critics feeling that a man so thoroughly master of his art, so
consummate a painter, must be wilfully affected in the treatment of
his subjects, his simple acceptance of nature appearing to them as a
pose. But it was not long before he was understood; and one has
only to read the very interesting memoir of M. Theuriet to see how
mistaken this view was, and how simply and naturally his art
developed from his early life and associations. It is seldom indeed
that one finds an artist so completely adjusted to his surroundings—
so much so that he is able to go back for his mature inspiration not
only to his first impressions, but to the very scenes and, in some
cases no doubt, the individuals who awakened them. As a rule an
artist nowadays is led in many directions before he finds himself.
Bastien-Lepage had his doubts and hesitations, of course, but they
were soon over, and almost from the start he seems to have decided
on his path.
The advantage of this to him in his work must have been
enormous, as any one who has painted in the country will know; for
villages contain no surplus population—every one has his work to
do; and the peasant is slow to understand, and distrustful of all that
lies outside his own experience: so that it is difficult, and in many
cases impossible, for an artist to get models in a village. But one can
imagine Lepage to have been friends with all his models, and that
his pictures excited as lively an interest (though, of course, on
different grounds) in Damvillers as in Paris; and it was, I think, due to
some extent to this, as well as to his own untiring energy, that he
was enabled to complete so much. As far as I am aware, he was
unique among contemporary artists in being so happily
circumstanced; and it is evidence of the simple sincerity of the man
that he found his ideal in the ordinary realities of his own experience:
feeling, no doubt, that beauty exists everywhere waiting for him who
has eyes to see.
It has been frequently said of Bastien-Lepage that he had no
feeling for beauty—or, at any rate, that he was indifferent to it; but as
it is impossible to arrive at any satisfactory definition of beauty, this
point cannot be discussed. Taking the word, however, in its obvious
and generally accepted meaning, that of personal beauty, it seems to
me that there is no fair ground for the charge; for such works as the
“First Communion,” the portrait of Sarah Bernhardt, and “Joan of
Arc,” all show a most refined and delicate appreciation of personal
beauty, and should surely have led his critics to consider whether the
man who painted them had not very good reasons for painting
people who were not beautiful, too. For all work cannot be judged
from one point of view; we recognize that a work of art is the
outcome of a personal impression, and that the artist’s aim is to give
expression to his views; and the deeper his insight into nature, the
greater the result. And yet, curiously enough, the fact that Bastien-
Lepage’s insight into nature was exceptionally deep and wide
renders it difficult to form a clear judgment, as his work appeals
equally from different points of view. His love of beauty, for instance,
seems to go hand-in-hand with a psychological, or even pathological
interest: and this equal prominence of different tendencies is a very
puzzling element in his work. We expect an artist to give us a
strongly personal view; but here is one who gives us something very
like an analysis, and whose personal view it is impossible to define—
and the premature ending of his career leaves it now for ever
doubtful which was the strongest bias of his mind. It seems to me
that his sympathies were so wide as to try and include everything,
and that he has helped to widen the bounds of beauty, by showing
its limitless possibilities. The words of Blake, “To see a world in a
grain of sand, and heaven in a wild flower,” suggest, I think, his
general feeling towards nature.
In spite of the wide range of his work and the extraordinary
versatility of his execution, he kept, as a rule, within certain
limitations of treatment. He did not care for the strong opposition of
light and shadow, and he seems almost to have avoided those
aspects of nature which depend for their beauty on the changes and
contrasts of atmosphere and light. All that side of nature which
depends on memory for its realization was left almost untouched by
him, and yet it is idle to suppose that so richly gifted a man could not
have been keenly sensible to all nature’s beauty; but I think he found
himself hedged in by the conditions necessary to the realization of
the qualities he sought. For in painting a large figure-picture in the
open air, the painter must almost of necessity limit himself to the
effect of grey open daylight. This he realized splendidly: at the same
time it may be said that he sought elaboration of detail perhaps at
the expense of effect, approaching nature at times too much from
the point of view of still-life. This is not felt in his small pictures, in
which the point of view is so close that the detail and general effect
can be seen at the same time; but in his large works much that is
charming in the highest degree when examined in detail, fails to
carry its full value to the eye at a distance necessary to take in the
whole work. This was the case with “Joan of Arc” in the Paris
Exhibition of two years ago; and it was instructive to compare this
picture with Courbet’s “Stone-breakers,” which hung near it on the
same wall. Courbet had generalized as much as possible—
everything was cleared away but the essentials; and at a little
distance Courbet showed in full power and completeness, while the
delicate and beautiful work in “Joan of Arc” was lost, and the picture
flat and unintelligible in comparison. No doubt Bastien-Lepage
worked for truth of impression and of detail too, but it is apparently
impossible to get both; and this seems to show that the building-up
or combining a number of facts, each of which may be true of itself
and to the others, does not in its sum total give the general
impression of truth. It is but a number of isolated truths. Bastien-
Lepage has carried his endeavour in this direction farther than any of
his predecessors—in fact it may be said that he has carried literal
representation to its extreme limit: so much so as to leave clearly
discernible to us the question which was doubtless before him, but
which has at any rate developed itself from his work, whether it is
possible to attain literal truth without leaving on one side much of
that which is most beautiful in nature? And further, the question
arises, whether literal truth is the highest truth. For realism, as an
end in art, leads nowhere; it is an impasse. Surely it is but the means
to whatever the artist has it in him to express.
I feel convinced that realism was not the end with Bastien-
Lepage. I believe that his contribution to art, great as it was, and
covering as it does an amount of work which might well represent a
whole life’s work instead of the work of a few short years, was but
the promise of his full power, and that, had he lived, his work would
have shown a wider range of nature than that of any other artist,
except perhaps Rembrandt. But it was not to be.
He gave his best, and the world is richer for his work; his name
will not die.
“Quiet consummation have;
And renowned be thy grave.”
GEORGE CLAUSEN.
MODERN REALISM IN PAINTING.
 The Little Sweep.
By Jules Bastien-Lepage.
 MODERN REALISM IN PAINTING.

Much has been written about Jean François Millet, and mostly from
two points of view. The picturesque surroundings of the plain of
Barbizon and the peasant’s blouse have tempted the sentimental
biographer to dwell on the personal note of poverty, which we now
know was not the dominant one in Millet’s life. The picturesque writer
has amplified, with more or less intelligence, reflections suggested
by the subjects of his pictures. In all this, the painter’s point of view,
which is, after all, the only one that matters, has, so far as its
expression in print is concerned, been overlooked and omitted.
The important fact about Millet is not that he struggled with
poverty, or that he expressed on canvas the dignity of labour, but
that he was a great artist. As corollaries, he was a great
draughtsman and a great colourist. He was gifted with the
comprehension in its entirety of the import of any scene in nature
which he wished to render. An unerring analysis enabled him to
select what were the vital constituents of such a scene, and exquisite
perceptions, trained by incessant labour, to render them in fitting
terms in accordance with the tradition which governs the use of each
material.
It may seem that the process here summarized is after all only
that which governs all art production, and that the work of the
second-rate and the ordinary differs only from that of the master in
the degree of capacity exercised. But this is not so. It differs totally in
kind. The conception, conscious or unconscious, of the nature and
aim of art is in the two cases different, and, as a consequence, the
practice is different.
It would be affectation to ignore that, for good or for evil, Paris is
the art-centre of European painting, and that the most serious
training in drawing and painting that is procurable on European lines
is procurable in Paris. I should therefore consider it a service of great
utility to serious art if it were possible to make clear the reasons for
my conviction that the tendency of the mass of exhibition painting in
France, and, by reflection, in England, has been in an inartistic
direction, and has led inevitably to the sterile ideal of the
instantaneous camera. And, on the other hand, that the narrow
stream of purely artistic painting, that has trickled its more
sequestered course parallel with the broad flood of exhibition work,
owes its vitality to a profound and convinced reverence for tradition.
For the illustration of that tradition I can find no more convenient
source than the work of Jean François Millet, and for a typical
monument of its disregard, the more fair to cite in that it is
respectable in achievement, the work of Bastien-Lepage affords me
a timely and perhaps the most appropriate example possible.
What, then, is the main difference? How did Millet work, and with
what objects? How did Lepage work, and what is it he strove to
attain?
To begin with, Millet, ninety-nine times out of a hundred, had seen
his picture happen somewhere in nature. Its treatment generally
involved complex difficulties of suggestion of movement, or at least
of energy, to say nothing of those created by the variety of lighting
and atmospheric effect; the management of sunlight, of twilight, of
the lighting of interiors. All these elements he was enabled, by
means of a highly-trained artistic memory, to retain and render in the
summary method which we call inspiration, and which has nothing in
common with the piecemeal and futile copying of nature of a later
school. Dealing with materials in their essential nature living and
fleeting, his execution was in the main separated from his
observation. His observation was thus uninterrupted by the
exigencies of execution, and his execution untrammelled by the
fortuitous inconveniences incident on the moment of observation,
and undisturbed, moreover, by the kaleidoscopic shifting of the
pictorial elements which bewilder and mislead the mere plein-airiste.
He did not say to the woman at the washtub, “Do as if you were
washing, and stay like that for me for four or five hours a day, while I
paint a picture from you.” Or to the reaper, “Stay like that with the
scythe drawn back, pretending to reap.” “La nature ne pose pas”—to
quote his own words. He knew that if figures in movement were to be
painted so as to be convincing, it must be by a process of cumulative
observation. This truth one of the greatest heirs of the great school
of 1830 has not been slow to understand, and it is to its further and
more exquisite development that we owe the profoundly learned and
beautiful work of Degas. His field of observation is shifted from the
life of the village and the labour of the plains, to the sordid toil of the
greenroom and the hectic mysteries of stage illumination; but the
artistic problem remains the same, and its solution is worked out on
the same lines.
Millet observed and observed again, making little in the way of
studies on the spot, a note sometimes of movement on a cigarette-
paper. And when he held his picture he knew it, and the execution
was the singing of a song learned by heart, and not the painful
performance in public of a meritorious feat of sight-reading. The
result of this was that his work has style—style which is at the same
time in the best traditions and strictly personal. No one has been
more imitated than Millet, and no one is more inimitable.
Holding in the hollow of his hand the secrets of light and life and
movement, the secrets of form and colour, learnt from the visible
world, he was equipped, like the great masters of old, for the
treatment of purely fanciful themes; and, when he painted a reluctant
nymph being dragged through the woods by a turbulent crowd of
cupids, he was as much at home as when he rendered the recurring
monotone of the peasant’s daily labours. My quarrel with the
gentlemen who escape from the laws of anatomy and perspective by
painting full-length portraits of souls, and family groups of
abstractions, is, not that they paint these things, but that they have
not first learnt something about the laws which govern the incidence
of light on concrete bodies. It might be well if they would discover
whether they can paint their brother, whom they have seen, before
they elect to flounder perennially in Olympus.
Let it also be noted here that the work of Jean François Millet
was, with scarcely an exception, free from a preoccupation with the
walls of an exhibition. The scale of his pictures and their key were