Nanomaterials

Processing and Characterization with Lasers

S. C. Singh, H.B. Zeng, Chunlei Guo, Weiping Cai

• Publisher: Wiley-VCH
• Year: 2012
• Print ISBN: 9783527327157
• eBook ISBN: 9783527646845
• Edition: 1
• Topic: Technology & Engineering
• Subtopic: Materials Science
• Index: Technology & Engineering

The first in-depth treatment of the synthesis, processing, and characterization of nanomaterials using lasers, ranging from fundamentals to
the latest research results, this handy reference is divided into two main sections. After introducing the concepts of lasers, nanomaterials, nanoarchitectures and laser-material interactions in the first three chapters, the book goes on to discuss the synthesis of various nanomaterials in vacuum, gas and liquids. The second half discusses various nanomaterial characterization techniques involving lasers, from Raman and photoluminescence spectroscopies to light dynamic scattering, laser spectroscopy and such unusual techniques as laser photo acoustic, fluorescence correlation spectroscopy, ultrafast dynamics and laser-induced thermal pulses.

The specialist authors adopt a practical approach throughout, with an emphasis on experiments, set-up, and results. Each chapter begins
with an introduction and is uniform in covering the basic approaches, experimental setups, and dependencies of the particular method on
different parameters, providing sufficient theory and modeling to understand the principles behind the techniques.

Chapter 1

Lasers: Fundamentals, Types, and Operations

Subhash Chandra Singh, Haibo Zeng, Chunlei Guo, and Weiping Cai

The acronym LASER, constructed from Light Amplification by Stimulated Emission of Radiation, has become so common and popular in every day life that it is now referred to as laser. Fundamental theories of lasers, their historical development from milliwatts to petawatts in terms of power, operation principles, beam characteristics, and applications of laser have been the subject of several books [1–5]. Introduction of lasers, types of laser systems and their operating principles, methods of generating extreme ultraviolet/vacuum ultraviolet (EUV/VUV) laser lights, properties of laser radiation, and modification in basic structure of lasers are the main sections of this chapter.

1.1 Introduction of Lasers

1.1.1 Historical Development

The first theoretical foundation of LASER and MASER was given by Einstein in 1917 using Plank's law of radiation that was based on probability coefficients (Einstein coefficients) for absorption and spontaneous and stimulated emission of electromagnetic radiation. Theodore Maiman was the first to demonstrate the earliest practical laser in 1960 after the reports by several scientists, including the first theoretical description of R.W. Ladenburg on stimulated emission and negative absorption in 1928 and its experimental demonstration by W.C. Lamb and R.C. Rutherford in 1947 and the proposal of Alfred Kastler on optical pumping in 1950 and its demonstration by Brossel, Kastler, and Winter two years later. Maiman's first laser was based on optical pumping of synthetic ruby crystal using a flash lamp that generated pulsed red laser radiation at 694 nm. Iranian scientists Javan and Bennett made the first gas laser using a mixture of He and Ne gases in the ratio of 1 : 10 in the 1960. R. N. Hall demonstrated the first diode laser made of gallium arsenide (GaAs) in 1962, which emitted radiation at 850 nm, and later in the same year Nick Holonyak developed the first semiconductor visible-light-emitting laser.

1.1.2 Basic Construction and Principle of Lasing

Basically, every laser system essentially has an active/gain medium, placed between a pair of optically parallel and highly reflecting mirrors with one of them partially transmitting, and an energy source to pump active medium. The gain media may be solid, liquid, or gas and have the property to amplify the amplitude of the light wave passing through it by stimulated emission, while pumping may be electrical or optical. The gain medium used to place between pair of mirrors in such a way that light oscillating between mirrors passes every time through the gain medium and after attaining considerable amplification emits through the transmitting mirror.

Let us consider an active medium of atoms having only two energy levels: excited level E₂ and ground level E₁. If atoms in the ground state, E₁, are excited to the upper state, E₂, by means of any pumping mechanism (optical, electrical discharge, passing current, or electron bombardment), then just after few nanoseconds of their excitation, atoms return to the ground state emitting photons of energy hν = E₂ − E₁. According to Einstein's 1917 theory, emission process may occur in two different ways, either it may induced by photon or it may occur spontaneously. The former case is termed as stimulated emission, while the latter is known as spontaneous emission. Photons emitted by stimulated emission have the same frequency, phase, and state of polarization as the stimulating photon; therefore they add to the wave of stimulating photon on a constructive basis, thereby increasing its amplitude to make lasing. At thermal equilibrium, the probability of stimulated emission is much lower than that of spontaneous emission (1 : 10³³), therefore most of the conventional light sources are incoherent, and only lasing is possible in the conditions other than the thermal equilibrium.

1.1.3 Einstein Relations and Gain Coefficient

Consider an assembly of N₁ and N₂ atoms per unit volume with energies E₁ and E₂(E₂ > E₁) is irradiated with photons of density ρ_ν = N hυ, where [N] is the number of photons of frequency ν per unit volume. Then the stimulated absorption and stimulated emission rates may be written as N₁ρ_vB₁₂ and N₂ρ_vB₂₁ respectively, where B₁₂ and B₂₁ are constants for up and downward transitions, respectively, between a given pair of energy levels. Rate of spontaneous transition depends on the average lifetime, τ₂₁, of atoms in the excited state and is given by N₂A₂₁, where A₂₁ is a constant. Constants B₁₂, B₂₁, and A₂₁ are known as Einstein coefficients. Employing the condition of thermal equilibrium in the ensemble, Boltzmann statistics of atomic distribution, and Planck's law of blackbody radiation, it is easy to find out B₁₂ = B₂₁, A₂₁ = B₂₁(8πhν³/c³), known as Einstein relations, and ratio, R = exp(hν/kT) − 1, of spontaneous and stimulated emissions rates. For example, if we have to generate light of 632.8 nm (ν = 4.74 × 10¹⁴ Hz) wavelength at room temperature from the system of He–Ne, the ratio of spontaneous and stimulated emission will be almost 5 × 10²⁶, which shows that for getting strong lasing one has to think apart from the thermal equilibrium. For shorter wavelength, laser, ratio of spontaneous to stimulated emission is larger, ensuring that it is more difficult to produce UV light using the principle of stimulated emission compared to the IR. Producing intense laser beam or amplification of light through stimulated emission requires higher rate of stimulated emission than spontaneous emission and self-absorption, which is only possible for N₂ > N₁ (as B₁₂ = B₂₁) even though E₂ > E₁ (opposite to the Boltzmann statistics). It means that one will have to create the condition of population inversion by going beyond the thermal equilibrium to increase the process of stimulated emission for getting intense laser light.

If a collimated beam of monochromatic light having initial intensity I₀ passes through the mentioned active medium, after traveling length x, intensity of the beam is given by I(x) = I₀e^−αx, where α is the absorption coefficient of the medium, which is proportional to the difference of N₁ and N₂. In the case of thermal equilibrium N₁

N₂ the irradiance of the beam will decrease with the length of propagation through the medium. However, in the case of population inversion, (N₂ > N₁) − α, will be positive and the irradiance of the beam will increase exponentially as I(x) = I₀e^kx, where k is the gain coefficient of the medium and may be given by k = (nN_dhν₂₁B₂₁)/c, where N_d is N₂ − N₁, c is speed of light, and n is refractive index of the medium.

1.1.4 Multilevel Systems for Attaining Condition of Population Inversion

Considering the case of two energy level system under optical pumping, we have already discussed that B₁₂ = B₂₁, which means that even with very strong pumping, population distribution in upper and lower levels can only be made equal. Therefore, optical as well as any other pumping method needs either three or four level systems to attain population inversion. A three level system (Figure 1.1a) irradiated by intense light of frequency ν₀₂ causes pumping of large number of atoms from lowest energy level E₀ to the upper energy level E₂. Nonradiative decay of atoms from E₂ to E₁ establishes population inversion between E₁ and E₀ (i.e., N₁ > N₀), which is practically possible if and only if atoms stay for longer time in the state E₁ (metastable state, i.e., have a long lifetime) and the transition from E₂ to E₁ is rapid. If these conditions are satisfied, population inversion will be achieved between E₀ and E₁, which makes amplification of photons of energy E₁ − E₀ by stimulated emission. Larger width of the E₂ energy level could make possible absorption of a wider range of wavelengths to make pumping more effective, which causes increase in the rate of stimulated emission. The three level system needs very high pumping power because lower level involved in the lasing is the ground state of atom; therefore more than half of the total number of atoms have to be pumped to the state E₁ before achieving population inversion and in each of the cycle, energy used to do this is wasted. The pumping power can be greatly reduced if the lower level involved in the lasing is not ground state, which requires at least a four level system (Figure 1.1b). Pumping transfers atoms from ground state to E₃, from where they decay rapidly into the metastable state E₂ to make N₂ larger than N₁ to achieve the condition of population inversion between E₂ and E₁ at moderate pumping.

Figure 1.1 Energy level diagram for (a) three- and (b) four level laser systems.

1.1.5 Threshold Gain Coefficient for Lasing

Laser beam undergoes multiple oscillations (through active medium) between pair of mirrors to achieve considerable gain before it leaves the cavity through partially reflecting mirror. Laser oscillation can only sustain in the active medium if it attains at least unit gain after a round-trip between mirrors and maintains it overcoming various losses inside the cavity. If we incorporate these losses, the effective gain coefficient reduces to k − υ, where υ is the loss coefficient of the medium. If round-trip gain G were less than unity, the laser oscillation would die out, while it would grow if the G value were larger than unity. Let us consider that the laser beam of intensity I₀ passes through the active medium, homogeneously filled in the length L between the space of two mirrors M₁ and M₂ with reflectivities R₁ and R₂, respectively. The beam of intensity I₀ initiates from the surface of M₁ and attains intensity I₁(I₁ = I₀exp(k − ϒ)L) after traveling a length L to reach at the surface of M₂. After reflection from M₂ and ...

Table of contents

• Cover
• Related Titles
• Title Page
• Copyright
• Preface
• List of Contributors
• Chapter 1: Lasers: Fundamentals, Types, and Operations
• Chapter 2: Introduction of Materials and Architectures at the Nanoscale
• Part I: Nanomaterials: Laser Based Processing Techniques
• Part II: Nanomaterials: Laser-Based Characterization Techniques
• Index