Vij D.R. Handbook of Applied Solid State Spectroscopy
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Contents xiii
10.5.3 AES Modifications and Combinations with
Hsiao-Lu Lee and Nolan T. Flynn
Baldassare Di Bartolo and John Collins
Other Techniques ......................................................................... 466
10.6 Auger Spectra: Direct and Derivative Forms ....................................... 466
10.7 Applications.......................................................................................... 468
10.7.1 Qualitative Analysis ..................................................................... 468
10.7.2 Quantitative Analysis ................................................................... 468
10.7.3 Chemical Information .................................................................. 472
10.7.4 Auger Depth Profiling.................................................................. 473
10.7.5 Auger Images and Linescans........................................................ 476
10.7.6 Research and Industry .................................................................. 477
10.8 Recent Advances .................................................................................. 479
10.8.1 Positron-Annihilation-Induced AES ............................................ 480
10.8.2 Auger Photoelectron Coincidence Spectroscopy ......................... 480
10.9 Conclusions .......................................................................................... 481
References .................................................................................................... 481
11. X-Ray Photoelectron Spectroscopy..................................................... 485
11.1 Introduction and Basic Theory ............................................................. 485
11.2 Historical Perspective........................................................................... 486
11.3 Instrumentation..................................................................................... 486
11.3.1 Vacuum System............................................................................ 487
11.3.2 X-Ray Source ............................................................................... 489
11.3.3 Electron Energy Analyzer ............................................................ 492
11.4 Sample Selection and Preparation........................................................ 492
11.4.1 Sample Charging.......................................................................... 493
11.4.2 X-Ray Beam Effects..................................................................... 495
11.5 Spectral Analysis.................................................................................. 496
11.5.1 Core Level Splitting ..................................................................... 498
11.5.2 Linewidths.................................................................................... 500
11.5.3 Elemental Analysis: Qualitative and Quantitative ....................... 500
11.5.4 Secondary Structure ..................................................................... 501
11.6 XPS Imaging ........................................................................................ 502
11.7 Angle-Resolved XPS............................................................................ 504
11.8 Recent Advances and Applications ...................................................... 504
11.9 Conclusions .......................................................................................... 506
References .................................................................................................... 506
12. Luminescence Spectroscopy ................................................................ 509
12.1 Introduction .......................................................................................... 509
12.1.1 Basic Concepts ............................................................................. 509
12.1.2 History.......................................................................................... 510
xiv Contents
12.6.1 Density of One-Electron States and Fermi Probability
12.2.1 Classical Bound, Radiating Electron............................................ 511
12.2.2 Quantum Mechanical Radiative Decay........................................ 513
12.2.3 Absorption and Emission ............................................................. 516
12.2.4 Absorption Coefficient and Absorption Cross-Section................ 518
12.3 Measurements and Techniques............................................................. 519
12.3.1 Absorption Spectra....................................................................... 519
12.3.2 Luminescence Spectra.................................................................. 521
12.3.3 Excitation Spectra ........................................................................ 522
12.3.4 Responses to Pulsed Excitation.................................................... 522
12.4 Localized Systems................................................................................ 523
12.4.1 Introduction.................................................................................. 523
12.4.2 The Hamiltonian of an Ion in a Solid........................................... 524
12.4.3 Rare Earth Ions in Solids.............................................................. 524
12.4.4 Transition Metal Ions in Solids .................................................... 528
12.4.5 Color Centers in Solids ................................................................ 535
12.5 Processes in Localized System Service................................................ 539
12.5.1 Introduction.................................................................................. 539
12.5.2 Radiative Decay ........................................................................... 540
12.5.3 Multiphonon Decay...................................................................... 542
12.5.4 Vibronic Transitions..................................................................... 545
12.5.5 Energy Transfer............................................................................ 547
12.5.6 Upconversion ............................................................................... 548
12.5.7 Line Broadening and Shifting with Temperature......................... 549
12.6 Delocalized Systems............................................................................. 551
Distribution .................................................................................. 551
12.6.2 Classification of Crystalline Solids .............................................. 552
12.6.3 Intrinsic Semiconductors.............................................................. 554
12.6.4 Doped Semiconductors ................................................................ 556
12.6.5 Model for a Doped Semiconductor .............................................. 557
12.7 Processes in Delocalized Systems ........................................................ 560
12.7.1 Direct Gap and Indirect Gap Semiconductors.............................. 560
12.7.2 Excitation in Insulators and Large Band Gap Semiconductors.... 561
12.7.3 Radiative Transitions in Pure Semiconductors ............................ 562
12.7.4 Doped Semiconductors ................................................................ 564
12.7.5 Radiative Transitions Across the Band Gap................................. 565
12.7.6 Non-Radiative Processes.............................................................. 566
12.7.7 p-n Junctions ................................................................................ 567
12.8 Direction of Future Efforts ................................................................... 571
12.8.1 Why Luminescence? .................................................................... 571
12.8.2 Challenges and Future Work........................................................ 571
References .................................................................................................... 574
Bibliography................................................................................................. 575
12.2 Spontaneous Emission, Absorption, and Induced Emission ................ 511
Contents xv
G. Geipel
14. Soft X-Ray Emission and Resonant Inelastic Scattering
E.J. Nordgren, S.M. Butorin, L.C. Duda, and J.-H. Guo
References
Alfons Schulte and Yu Guo
13. Laser-Induced Fluorescence Spectroscopy ........................................ 577
13.1 Introduction .......................................................................................... 577
13.2 Experimental Setup .............................................................................. 578
13.3 Fluorescence Spectroscopy of Minerals............................................... 579
13.4 Fluorescence Spectroscopy of Surface Species and in Solid Phases.... 584
13.5 Fluorescence Spectroscopy of Frozen Samples.................................... 586
13.6 Fluorescence Spectroscopy of Non-Actinide Solid Matrices............... 589
13.7 Outlook................................................................................................. 591
References .................................................................................................... 591
Spectroscopy ......................................................................................... 595
14.1 Introduction .......................................................................................... 595
14.2 Properties of X-Ray Spectra................................................................. 597
14.3 Resonant Inelastic X-Ray Scattering.................................................... 602
14.4 Experimental Techniques ..................................................................... 605
14.4.1 Grating Spectrometers for Soft X-Ray Emission......................... 605
14.4.2 Samples at Ambient Conditions................................................... 608
14.5 Applications.......................................................................................... 609
14.5.1 Surfaces, Interfaces, and Thin Films............................................ 609
14.5.2 Nano Structures............................................................................ 615
14.5.3 Transition Metal Systems............................................................. 619
14.6 Summary .............................................................................................. 654
.
.............................................................................................
654
15. Laser Raman Spectroscopy ................................................................. 661
15.1 Introduction .......................................................................................... 661
15.2 Spontaneous Raman Scattering ............................................................ 663
15.3 Experimental Approaches .................................................................... 666
15.4 Applications.......................................................................................... 670
15.4.1 Glasses for Raman Gain............................................................... 671
15.4.2 Chalcogenide Glasses................................................................... 673
15.4.3 Chalcogenide Thin Films—Waveguide Raman........................... 675
15.4.3 High-Pressure Raman Spectroscopy of Proteins.......................... 677
15.4.4 Micro-Raman Spectroscopy......................................................... 680
15.5 Conclusions and Outlook ..................................................................... 685
References .................................................................................................... 685
xvi Contents
16.2 Occurrence, Production, and Optical
Properties
of Aligned Solid Samples
16.3.1 Optical Spectroscopy with Linearly Polarized Light:
16.3.4 Transition Moment Directions and Reduced Spectra:
16.3.5 Transition Moment Directions: Molecules
Peter W. Thulstrup and Erik W. Thulstrup
16. Polarization Spectroscopy of Ordered Samples ................................ 689
16.1 Introduction .......................................................................................... 689
16.1.1 Linearly Polarized Light............................................................... 689
16.1.2 Transition Moment Directions ..................................................... 690
16.1.3 Spectroscopy with Linearly Polarized Light................................ 694
.....................................................................
696
16.2.1 Perfectly and Partially Aligned Samples...................................... 696
16.2.2 Solutes in Partially Aligning Solvents.......................................... 697
16.3 One-Photon Spectroscopy: Linear Dichroism...................................... 699
Experimental Needs ..................................................................... 699
16.3.2 Mathematical Descriptions of Aligned, Uniaxial Samples .......... 700
16.3.3 LD Spectra of Aligned, Uniaxial Samples ................................... 702
Symmetrical Molecules................................................................ 704
of Lower Symmetry ..................................................................... 715
16.3.6 Non-Uniaxial Samples ................................................................. 720
16.4 Two-Photon Spectroscopy.................................................................... 721
16.5 Conclusions .......................................................................................... 726
References .................................................................................................... 726
CONTRIBUTORS
Chris Arumainayagam, Wellesley College, MA 02481, USA, Tel: +1-781-
283-3326
Email: carumain@wellesley.edu
Baldassare Di Bartolo, Department of Physics, Boston College, Chestnut
Hill, MA 02467, USA, Tel: +1-617-552-3601
E-mail: dibartob@bc.edu
Tito José Bonagamba, Institute de Física de São Carlos, Universidade de São
Paulo – Brazil, Tel: +55 16 3373 9871
E-mail: tito@if.sc.usp.br
S.M. Butorin, Department of Physics, Uppsala University, Uppsala, Sweden
J.M Cadogan, School of Physics, The University of New South Wales,
Sydney, NSW2052, Australia, Tel: +61-2-9385-5203
E-mail: J.Cadogan@unsw.edu.au
John Collins, Department of Physics, Wheaton College, Norton, MA 02766,
USA, Tel: +1-508-286-3976
Email: jcollins@wheatoncollege.edu
Antony R. Crofts, Department of Biochemistry, University of Illinois at
Urbana-Champaign, Urbana, IL 61801 USA, Tel: +1-217 333-2043
E-mail: a-crofts@life.uiuc.edu
Eduardo Ribeiro deAzevedo, Institute de Física de São Carlos, Universidade
de São Paulo - Brazil, Tel: +55 16 3373 8086
E-mail: azevedo@if.sc.usp.br
Sergei Dikanov, Department of Veterinary Clinical Medicine, University of
Illinois at Urbana-Champaign, Urbana, IL 61801, USA, Tel: +1-217-333-
3776
E-mail: dikanov@uiuc.edu
L.C. Duda, Department of Physics, Uppsala University, Uppsala, Sweden
Esmaeil Enjilela, Faculty of Mechanical Engineering, K.N. Toosi University
of Technology, Tehran, Iran
Nolan T. Flynn, Wellesley College, Wellesley, MA 02481, USA, Tel: +1-
781-283-3097; FAX: +1-781-283-3642
Email: nflynn@wellesley.edu
Albert Furrer, Laboratory for Neutron Scattering, ETH Zurich &PSI
Villigen, CH-5232 Villigen PSI, Switzerland, Tel:+41-56-310-2088
G. Geipel, Institute of Radiochemistry, Forschungszentrum Rossendorf,
Dresden, Germany, Tel: +49-351 260 2306
E-mail: G.Geipel@fz-ossendorf.de
xviii Contributors
Richard P. Gunawardane, Wellesley College, Wellesley, MA 02481, USA,
Tel: +1-781 283 3530
E-mail:rgunawar@Wellesley.edu
J.-H. Guo, Lawrence Berkeley National Laboratory, Berkeley, CA 94720,
USA
Yu Guo, Department of Physics and College of Optics and Photonics–
CREOL, University of Central Florida, Orlando, FL 32816-2385, USA
K.W. Hipps, Department of Chemistry and Materials Science Program,
Washington State University, Pullman, WA 99164-4630, USA, Tel: +1-509-
335-3033
E-mail: hipps@wsu.edu
Farhang Honarvar, Faculty of Mechanical Engineering, K.N. Toosi
University of Technology, Tehran, Iran, Tel: +98-21-734-3300
Email: honarvar@mie.utoronto.ca
Neena Jaggi, Kurukshetra University; Kurukshetra, India Tel:+91-1744-291-
379
E-mail: neena_jaggi@rediffmail.com
Lowell D. Kispert, Chemistry Department, The University of Alabama,
Tuscaloosa, Alabama, USA, Tel: +1-205-348-7134
E-mail: lkispert@bama.ua.edu
Hsiao-Lu Denise Lee, Department of Chemistry, Stanford University,
Stanford, CA 94305-5080, USA
Tel: +1-650-723-2501
Email: hsiaolu@stanford.edu
E.J. Nordgren, Department of Physics, Uppsala University, Uppsala,
Sweden, Tel: +46-18471-3554
E-mail: joseph@fysik.uu.se
Lidia Piekara-Sady, Institute of Molecular Physics, Polish Academy of
Sciences, 60-179 Poznan, Poland
E-mail: lpsady@tlen.pl
Andrew Podlesnyak, Laboratory for Neutron Scattering ETHZ & PSI, CH-
5232 Villigen PSI, Switzerland, Tel: +41 56 310 4613
E-mail: andrew.podlesnyak@psi.ch
D.H Ryan, Department of Physics, McGill University, Montreal
(Quebec)H3A 2T8, Canada, Tel: +1-514-398-6534
E-mail: dominic@physics.mcgill.ca
Alfons Schulte, Department of Physics and College of Optics and
Photonics
– CREOL, University of Central Florida, Orlando, FL 32816-2385,
USA, Tel:
+1-407-823-5196
E-mail: afs@physics.ucf.edu
Contributors xix
Bryan H. Suits, Physics Department, Michigan Technological University,
Houghton, MI 49931, USA Tel: +1-906-487-2093
E-mail: suits@mtu.edu
Erik W. Thulsrup, Dept. of Life Sciences and Chemistry, Roskilde
University POB 260, DK-4000 Roskilde, Denmark, Tel: +45-4674-2709
E-mail: ewt@ruc.dk
Peter W. Thulstrup, Department of Natural Sciences, The Royal Veterinary
and Agricultural University, Th. 40. DK-1871 Frederiksberg, Denmark, Tel:
+45-3528-2464
E-mail: pwt@kvl.dk
D.R. Vij, Kurukshetra University; Kurukshetra, India Tel: +91-1744-238-816
E-mail: drvkuk@rediffmail.com
CHAPTER 1
NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY
Eduardo Ribeiro deAzevedo and Tito José Bonagamba
Instituto de Física de São Carlos – Universidade de São Paulo – Brazil
1.1 INTRODUCTION
After the development during the last 30 years of methods such as magic-
angle spinning, multiple-resonance experiments (cross-polarization, high
power decoupling, etc.), multiple pulses techniques, and multidimensional
spectroscopy, pulsed solid state nuclear magnetic resonance (NMR) is among
the most important experimental tools for studying physical and chemical
properties of new materials in the solid-state.
In this chapter, we discuss some basic aspects of the NMR methodology
and show some applications of the methods for studying molecular dynamics
and local structure in solid materials. Despite the fact that the methods and
applications presented in this chapter are predominantly related to organic
materials (polymers and derivatives, and small organic molecules) with some
extensions to inorganic materials (glasses, ionic conductors, etc.), several
basic aspects of advanced solid state NMR discussed here can be extended for
understanding other NMR techniques necessary for studying other kinds of
solid materials [1–9]. Due to the limitations of space, our discussions will be
allows the application of a large number of different techniques for
understanding their molecular dynamics and local conformation. In writing
the introduction of this chapter we have used as references several classic
books of modern solid state NMR [1–9] and quantum mechanics [10].
1.2 PROPERTIES OF NUCLEAR SPINS
Nuclear magnetic resonance is a phenomenon that occurs for nuclear spins
that possess magnetic moment and angular momentum
P
G
and
J
,
G
respectively.
namely, organic materials, particularly polymers and derivatives, which
focused to NMR methods for studying an important class of solid materials,
1. Nuclear Magnetic Resonance Spectroscopy
2
The relationship between both moments is µ Ȗ
J
G
G
, where is the
gyromagnetic ratio. In terms of quantum mechanics the angular momentum
J
G
is defined by ,
J
I
GG
= where
I
G
nuclear spin. The magnetic moment is quantized according to the usual
quantization of the angular momentum, i.e., the magnitude of the magnetic
moment is given by
µ Ȗ 1II
G
= [11]. The allowed components of µ
G
in
the direction of a magnetic field along the z direction (Zeeman interaction) are
given by
µ Ȗ
zz
I = .
z
I is the spin quantum number taking
21I values from
–I to +I, and I can take only integer or semi-integer values 1/2, 1, 3/2, 2,.…
Additionally, nuclei presenting
1/2I ! have also an electric quadrupole
moment.
1.3 NUCLEAR SPIN INTERACTIONS IN SOLIDS
The nuclear spin Hamiltonian involves interactions that are related to the
magnetic and electric properties of the nuclei and the experimental conditions
of the experiment. Some terms determine the intensity of the signal, while
others define the position and the shape of the spectral lines [1, 2, 7].
The nuclear spin Hamiltonian can be separated into two important groups:
internal and external interactions. The external interactions are associated to
the coupling of the nuclear spin magnetic moment
µ Ȗ I
G
G
=
with the static
magnetic field
00
ˆ
BBz
G
(Zeeman effect) and with the oscillating magnetic
radio frequency (rf) field applied perpendicularly to the static field
rf 1 rf rf
ˆˆ
cos Ȧ sin ȦBBt t tx t ty
ªº
II
¬¼
G
,
(1.1)
which induce the transitions between adjacent levels. The Hamiltonians for
both interactions are expressed by:
000
µ ȖȦ
zzz
HB BII
G
G
==
(1.2)
and
rf rf
µHB
G
G
.
(1.3)
For special excitation procedures (transition-selective, multitransition, or
multiple quantum excitations) the rf field may be amplitude-, frequency-,
and/or phase-modulated through the manipulation of the parameters
1
Bt,
rf
Ȧ , and
tI , respectively. Both external interactions dominate the behavior
of the spin system, but in general they do not contain the structural and
dynamic information, which are directly related to the internal nuclear spin
interactions.
The internal interactions are associated to the couplings of the nuclear
spins with, for example, magnetic fields originated from the orbital motion of
Ȗ
is a dimensionless operator denominated
1.3 Nuclear Spin Interactions in Solids
3
other nuclear spins through their magnetic dipole moments (dipolar
interaction), and the electric field gradients through their electric quadrupole
moments (quadrupolar interaction). Therefore, the internal Hamiltonian can
be written as a sum of several independent terms, which will be described in
the following items, and where we will assume that all the spin interactions
can be represented by second rank Cartesian tensors in the following way [2]:
x
xxyxz x
y z yx yy yz y
zx zy zz z
A
AA S
HIAS I I I A A A S
A
AA S
ªº
ªº
«»
«»
ªº
«»
¬¼
«»
«»
«»
¬¼
¬¼
.
(1.4)
Chemical Shift. The chemical shift Hamiltonian is given by:
CS 0 0
µ ıȖıHBIB
GGG
G
= ,
(1.5)
where
ı
is a second order tensor that represents the proportionality factor
between
0
B
G
and the magnetic fields originated along the directions x, y, and z
from the orbital motion of the electrons induced by the static magnetic field.
Assuming that
00
ˆ
BBz
G
, the chemical shift Hamiltonian results in
CS 0
Ȗı ı ı
xxz yyz zzz
HIIIB = .
(1.6)
The induced magnetic fields are very small compared to
0
B
G
, consequently
the chemical shift parameters
ı
ij
are of the order of 10
–6
, resulting in shifts
of the Zeeman energy levels on the order of parts per million (ppm).
Therefore, the chemical shift can be treated as a first order perturbation with
respect to the Zeeman interaction, and the effective Hamiltonian can be
truncated and written as follows [7]:
CS 0
Ȗı
zzz
HIB = .
(1.7)
Taking into consideration both Zeeman and chemical shift interactions
gives the full Hamiltonian:
CS 0
Ȗ 1 ı
zzzz
HH H B I = .
(1.8)
Dipolar Interaction. The classical interaction energy between two magnetic
moments
1
µ
G
and
2
µ
G
is [6]
12
12
35
3µ µ
µµ
rr
E
rr
GGG G
GG
,
(1.9)
where
r
G
is the distance vector between
1
µ
G
and
2
µ
G
. To write the dipolar
Hamiltonian we take
11
µ Ȗ I
G
G
= and
22
µ Ȗ I
G
G
= , where we assumed that the
gyromagnetic factors and spins may be different. The general dipolar
contribution to the Hamiltonian for N spins then becomes
the electrons induced by the static magnetic field (chemical shift interaction),
GG
x