Electrodynamics at Quantum Phase Transitions High Frequency Spectroscopy on Ferromagnetics

Thesis Presented to the Academic Faculty by Diana Geiger

03/29/2011

First Reader: Second Reader:

Prof. Dr. Martin Dressel Prof. Dr. J org Wrachtrup

1. Physikalisches Institut Universit at Stuttgart Pfaenwaldring 57, 70550 Stuttgart

Contents
1 Zusammenfassung 2 Introduction 3 Theoretical Background 3.1 3.2 3.3 3.4 Interaction of Electromagnetic Radiation with Metals . . . . . . . . . . . . . . . 3.1.1 Drude Model and Extended Drude Model . . . . . . . . . . . . . . . . . . Ferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 3 5 5 6 9

Ferromagnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 Quantum Criticality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 3.4.1 3.4.2 Fermi Liquid Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Quantum Phase Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . 15 19

4 Measurement Setups and Techniques 4.1 4.2

Ranges and Techniques in Optical Spectroscopy . . . . . . . . . . . . . . . . . . . 19 Microwave Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 Small Cryostat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 Transmission and Corbino Geometries . . . . . . . . . . . . . . . . . . . . 21 Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 MW Measurement Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . 27 THz Spectrometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 THz Transmission Measurements . . . . . . . . . . . . . . . . . . . . . . . 31 THz Phase Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 THz Measurement Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . 37 39

4.3

THz Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 4.3.1 4.3.2 4.3.3 4.3.4 4.3.5

5 Samples 5.1 5.2 5.3

Permalloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 Heusler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 Sr1x Cax RuO3 Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

iii

Contents 6 FMR: Results and Discussion 6.1 6.2 6.3 43

Reference Measurements and Permalloy . . . . . . . . . . . . . . . . . . . . . . . 43 Heusler Compound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 SrRuO3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 53

7 Sr1x Cax RuO3 : Results and Discussion 7.1 7.1.1 7.1.2 7.2 7.2.1 7.2.2

Microwave Spectrometer Results . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 Microwave Measurements of Samples on SrTiO3 Substrate . . . . . . . . . 54 Microwave Measurements of SrRuO3 on MgO . . . . . . . . . . . . . . . . 56 Problems with the rst CaRuO3 on NdGaO3 Sample . . . . . . . . . . . . 60 THz Results for SrRuO3 , Sr0.6 Ca0.4 RuO3 , Sr0.2 Ca0.8 RuO3 and CaRuO3 . 62 71

THz Spectrometer Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

8 Summary and Outlook

iv

List of Figures
2.1 phase diagram of Sr1x Cax RuO3 and previously reported non-Fermi-liquid behavior (purple areas). Diagram: [4], NFL phases: [4], [5], [6], [7]) . . . . . . . . . 3.1 3.2 frequency dependent conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . dierent types of magnetic order. Ferromagnet: parallel magnetic moments; antiferromagnet: antiparallel magnetic moments, magnetizations of the two sublattices cancel each other; ferrimagnet: antiparallel magnetic moments, magnetizations of the two sublattices have dierent absolute values. . . . . . . . . . . . 3.3 energy displacement of the subbands in an external magnetic eld (of downward direction). The dotted line denotes the position of the bands in zero eld. The total magnetization is the net eect produced by the states in the blue region. . . 10 3.4 4.1 4.2 4.3 phase diagram of a second order quantum phase transition as expected from theory 16 energy scales of some correlated electron phenomena [19] . . . . . . . . . . . . . . 19 open continuous ow cryostat with HP 8510C microwave source, test set, network analyzer, temperature controller and multimeter . . . . . . . . . . . . . . . . . . 20 sampleholders for broadband microwave transmission (left picture ) and reection (right picture ) measurements. The transmission sample holder has two connectors for two coaxial cables; ths signal ows through the sample, which is located in the middle. Only one coaxial cable goes into the reection sample holder from the back, a spring presses the sample against the contacts from the front side. The small drill holes on the front side are spots for temperature sensors and heaters 21 4.4 4.5 4.6 4.7 4.8 schematic view of a Corbino sampleholder as used in the reection experiments [20] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 eld distributions of the TEM mode in a coaxial waveguide (left side) and a strip transmission line (right side) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 schematic view of a broadband transmission sample arrangement as used in our experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 error model scheme for reection microwave measurements. S11 is the real reectivity of the sample, S11,m the measured one . . . . . . . . . . . . . . . . . . . 24 Smith chart with Short, Open and Load locations in the complex plane (empty Smith chart from www.wikipedia.de) . . . . . . . . . . . . . . . . . . . . . . . . . 25 9 3 7

List of Figures 4.9 output power of the dierent THz radiation backward oscillator (BWO) sources [23] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 4.10 interferometer setup used for transmission and phase measurements . . . . . . . 30 4.11 frame and sampleholder used for THz measurements: picture a shows the side facing the incoming beam, pictures b, c and d show the arrangement of frame, aperture and samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 4.12 diagram showing the dierent chambers of the bath cryostat used for THz measurements (drawing created by the mechanical workshop of the physics department, university of Stuttgart) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 4.13 transmission raw data of CaRuO3 on a NdGaO3 substrate of dierent BWOs at 300 K (logarithmic scale) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 4.14 reected and transmitted elds through a slab of dielectric material . . . . . . . 33

4.15 polarizations of the E vector in dierent interferometer sections (red arrows) [23] 36 4.16 scheme of the THz data analysis procedure . . . . . . . . . . . . . . . . . . . . . 38 5.1 5.2 crystal structure of Heusler alloy Co2 CrAl[29] and layered structure of Heusler samples CCFA429 and CCFA430 [28] . . . . . . . . . . . . . . . . . . . . . . . . . 40 left side: distorted perovskite structure of SrRuO3 and CaRuO3 consisting of RuO6 octahedra and Sr or Ca ions [31]. Ru atoms: purple, O atoms: red, Ca or Sr atoms: yellow right side: metalorganic aerosol deposition scheme [32] . . . . 41 5.3 temperature-dependent dc resistivity of the four high quality samples on NdGaO3 (data: courtesy of M. Schneider) . . . . . . . . . . . . . . . . . . . . . . . . . . . 42 6.1 6.2 6.3 6.4 empty setup and NiCr transmission measurements, normalized to maximum magnetic eld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 transmission (left side) and reection (right side) measurements of the Permalloy sample, normalized to the maximum eld data . . . . . . . . . . . . . . . . . . . 44 surface plot of the Permalloy FMR data . . . . . . . . . . . . . . . . . . . . . . . 45 CCFA transmission spectra as measured prior to normalization and analysis. As examples, the maximum (160 mT), one intermediate (70 mT) and one low (25 mT) magnetic eld was plotted. Inset: Detail of unprocessed spectra in proximity of the FMR resonance region, 5 GHz - 8 GHz . . . . . . . . . . . . . . 46 6.5 left side: transmission spectra normalized to maximum magnetic eld at 200 K right side: grayscale plot; the used spectra were measured at 200 K and normalized to maximum magnetic eld . . . . . . . . . . . . . . . . . . . . . . . . 47 6.6 3D surface plot of room temperature transmission spectra normalized to the next higher magnetic eld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

vi

List of Figures 6.7 black points and curves: dependence of the FMR frequency on static magnetic eld at temperatures of 150 K, 200 K, 250 K and 300 K; blue squares: resonance frequencies, calculated from eq. 3.43 and saturation magnetization values from [38] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 6.8 CCFA SQUID magnetization measurements published in [36] and magnetization ratios calculated from microwave measurements. The samples CCFA 429 and CCFA 430 correspond to the black curve in the diagram . . . . . . . . . . . . . . 49 6.9 left side: magnetic eld dependent reection measurements of SrRuO3 on MgO at 70 K. The corrected reection coecient S22 was normalized to the spectrum of maximum magnetic eld. right side: magnetic eld dependent transmission measurements of SrRuO3 on MgO at 70 K. Like for the other materials, all transmission spectra were normalized to the spectrum of maximum magnetic eld. 50 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 analysis procedure example; usually performed electronically by our Labview analysis routine (SrRuO3 on MgO spectra) . . . . . . . . . . . . . . . . . . . . . 53 real part of the impedance for CaRuO3 on SrTiO3 and SrRuO3 on SrTiO3 . . . . 54 real and imaginary parts of the conductivity for CaRuO3 on SrTiO3 . . . . . . . 55 real and imaginary parts of the conductivity for SrRuO3 on SrTiO3 . . . . . . . . 55 real and imaginary parts of the conductivity for CaRuO3 and SrRuO3 on SrTiO3 56 real and imaginary parts of the conductivity of SrRuO3 on MgO . . . . . . . . . 57 surface plot of the resistivity of SrRuO3 on MgO from 80 K to 300 K; the arrow indicates the kink in the resistivity at low frequencies . . . . . . . . . . . . . . . . 57 temperature dependence of the resistivity at dierent frequencies, the arrows indicate the location of the kink . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 example of transmission and phase data for Sr0.2 Ca0.8 RuO3 for 300 K and 5 K. All samples were measured at the same frequencies at several temperatures between 300 K and 5 K. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 7.10 measurement positions on the CaRuO3 on NdGaO3 sample . . . . . . . . . . . . 60 7.11 transmission spectra of the dierent sample spots . . . . . . . . . . . . . . . . . . 61 7.12 real and imaginary part of the conductivity for the CaRuO3 sample . . . . . . . 61 7.13 normalized resistivity data for all four samples: data obtained from THz data in the region of 5 cm1 (black single points) and dc resistivity curve measured by M. Schneider (gray) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 7.14 real parts of the conductivity for all samples on NdGaO3 . . . . . . . . . . . . . . 63 7.15 imaginary parts of the conductivity for all samples on NdGaO3 . Note the dierent scale for SrRuO3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 7.16 scattering rates for all four samples . . . . . . . . . . . . . . . . . . . . . . . . . . 67 7.17 eective mass ratios for all four samples . . . . . . . . . . . . . . . . . . . . . . . 68

vii

1 Zusammenfassung
Ferromagnetische Stoe und ihre Phasen uberg ange sind sowohl von theoretischer als auch von experimenteller Seite her interessant: F ur viele Ph anomene gibt es bisher keine zufriedenstellenden theoretischen Modelle und Vorhersagen. Gleichzeitig werden viele magnetische Materialien als Kandidaten f ur zuk unftige technische Anwendungen gehandelt. Ein tieferes Verst andnis und aufkl arende Messungen sind daher w unschenswert. In dieser Arbeit wurden im Wesentlichen zwei Ph anomene an ferromagnetischen Materialien mit Mikrowellen- und THz-Spektroskopie untersucht: Zum Einen wurde die ferromagnetische Resonanz (FMR) von Permalloy (Ni80 Fe20 ) und einer Heusler Legierung (Co2 Cr0.6 Fe0.4 Al) mit breitbandiger Transmissions - Mikrowellenspektroskopie gemessen. F ur Permalloy ergaben sich Resonanzfrequenzen zwischen 3.5 GHz und 9 GHz f ur Magnetfelder zwischen 20 mT und 148 mT, f ur die Heusler Legierung Resonanzfrequenzen zwischen 5.5 GHz und 9 GHz bei denselben Magnetfeldern. Aus den Resonanzfrequenzen und den Halbwertsbreiten der Resonanzen ergab sich eine Gilbert-D ampfung von = 0.097 0.37. Das ebenfalls untersuchte Material SrRuO3 zeigte keine FMR in diesem Frequenzbereich. Dies k onnte darauf hindeuten, dass die FMR in diesem Material in einem sonst ungew ohnlichen Frequenzbereich liegt, wie es Kerr-Messungen bei etwa 250 GHz nahelegen [1]. F ur eine D unnlm-Probengeometrie, wie sie in dieser Arbeit durchweg benutzt wurde, konnte breitbandige Reektions-Mikrowellenspektroskopie in keinem Material eine FMR au osen. Da FMR mit dieser Technik an Volumenproben erfolgreich gemessen wurde [2], dieselben Proben in Transmission aber eine eindeutige FMR zeigen, scheint dies durch Kombination von d unnen Filmen und der Reektions-Messmethode begr undet zu sein. Weiterhin wurden Messungen der frequenzabh angigen Leitf ahigkeit am System Sr1x Cax RuO3 durchgef uhrt. Die Curie-Temperatur des Ferromagneten SrRuO3 l asst sich durch Dotierung mit Kalzium unterdr ucken. Bei einem Kalziumaneteil von etwa 70% kommt es zu einem Quan tenphasen ubergang [3] mit der Ubergangstemperatur von 0 K, der im Unterschied zu klassischen Phasen uberg angen nicht von thermischen, sondern von Quanten-Fluktuationen getrieben wird. Im Phasendiagramm eines solchen quantenkritischen Systems werden auch bei endlichen Temperaturen Auswirkungen dieser Quanten-Fluktuationen in Gestalt neuartiger Phasen und unkonventionellen Verhaltens erwartet. Diese interessanten Bereiche treten bei sehr niedrigen Energien auf und sollten mit optischen Methoden erfasst werden k onnen. Daher sind in den entsprechenden Experimenten sehr niedrige Energien im Mikrowellen- und THz-Bereich n otig. W ahrend bei breitbandiger Mikrowellenspektroskopie das Signal durch Koaxialkabel an einen Netzwerkanalysator gesendet wird, handelt es sich bei der verwendeten Frequenzdom anen THz

1 Zusammenfassung Spektroskopie um ein quasioptisches Messverfahren mit Linsen und Strahlteilern. Es wurden insgesamt sieben Proben bei Temperaturen zwischen 2 K und 300 K untersucht. Davon waren zwei auf SrTiO3 -Substrat gewachsen, eine auf MgO und vier Proben sehr hoher Qualit at auf NdGaO3 . Es wurden vier verschiedene Materialien gemessen, einerseits die reinen Stoe SrRuO3 und CaRuO3 , andererseits zwei dotierte Proben mit 40% Kalzium und 80% Kalzium. Es ergab sich f ur SrRuO3 und die beiden dotierten Stoe ein Verhalten, das gr otenteils mit einer einfachen Drude-Leitf ahigkeit f ur Metalle erkl art werden kann. F ur CaRuO3 ergibt sich ein pl otzlicher Abfall der Leitf ahigkeit (sowohl im Real- als auch im Imagin arteil) bei etwa 10 cm1 f ur Temperaturen unter 30 K. Dies kann h ochstens durch mehrere Drudebeitr age erkl art werden, von denen einer eine u beraus geringe Streurate aufweist. Mit Blick auf das Verhalten der anderen Proben kann dies jedenfalls weder mit einem einfachen metallischen Drudeverhalten nocht mit einem Fermi ussigkeitsverhalten, welches zus atzlich zum Drudemodell einen frequenzabh angigen Anteil in die Streurate einbringt, erkl art werden und k onnte auf eine m ogliche nicht-Fermi ussigkeitsphase, wie sie auch schon in Messungen der Gleichstromleitf ahigkeit [3] f ur CaRuO3 gefunden wurde, hindeuten.

2 Introduction
Magnetism, magnetic ordering eects, and their phase transitions are intensively investigated topics both theoretically and experimentally. Many aspects and eects are still to be understood and integrated into existing physical models in order to broaden our knowledge of condensed matter physics. At the same time, magnetic materials have become important parts in technical applications like data storage devices and are promising candidates for future technologies like spintronics. It is therefore important to investigate the properties of such materials. In this work, two dierent aspects of magnetic phenomena were addressed with low-energy optics. When the itinerant ferromagnet SrRuO3 is doped with Ca, its Curie temperature is suppressed from 160 K (no doping) to 0 K (70% to 80% doping). This results in a so-called quantum phase transition, which takes place at 0 K and is driven by quantum uctuations. The eects of these quantum uctuations are expected to be measurable also at nite temperatures and lead to novel phases and unconventional physical behavior. The Fermi liquid theory by Landau

Figure 2.1: phase diagram of Sr1x Cax RuO3 and previously reported non-Fermi-liquid behavior (purple areas). Diagram: [4], NFL phases: [4], [5], [6], [7])

[8] is the established model for metals at low energies, but quantum critical behavior (driven by quantum uctuations) does not t into this framework and is non-Fermi-liquid-like. While many quantum phase transitions are studied in antiferromagnets, there are only few well-known ferromagnetic quantum critical systems [9]. As shown in g. 2.1, the Sr1x Cax RuO3 system is

2 Introduction a very promising object on which to study the inuences of quantum uctuations on itinerant ferromagnets. Fig. 2.1 indicates dierent regions in the phase diagram, where non-Fermi liquid behavior has been reported. From theory it is expected that the most interesting phenomena occur at low energies: quantum criticality as well as the Fermi liquid regime itself are only present at low energies. For that reason it is crucial to have low temperatures on the one hand, and, in the case of (optical) spectroscopy, low frequencies on the other. In the present study, microwave and THz spectroscopy were used to investigate the phase diagram of Sr1x Cax RuO3 from room temperature down to 5 K in order to obtain information on the electronic properties. Besides the quantum phase transition and quantum criticality, the material SrRuO3 shows another surprising feature: a ferromagnetic resonance was reported in that material at an unconventionally high frequency of 250 GHz [1]. Usually, a resonance frequency in the 1 GHz to 20 GHz region would be expected. Microwave spectroscopy is a very well-suited tool for the detection of ferromagnetic resonance and we tried to apply it to SrRuO3 and two other interesting ferromagnetic materials for this purpose. These other materials were Permalloy (used as a reference sample) and a Heusler alloy. Heusler alloys have recently become very promising materials for spintronics, and therefore their magnetization dynamics should be investigated thoroughly. For both spectroscopic methods, microwaves and THz, thin lm samples are used. From the raw data we usually determine the frequency-dependent conductivity, which contains the information on the electrodynamics of the respective system.

3 Theoretical Background

3.1 Interaction of Electromagnetic Radiation with Metals

Generally, electromagnetic radiation interacts with matter by generating some response inside the system. Here the physically relevant quantities, the elds E , B , D and H , have to provide a solution to Maxwells equations in presence of matter: 1 B c t B 1 D H c t D E+ = 0 = 0 4 = j c = 4 (3.1) (3.2) (3.3) (3.4)

It is to be noted that the charge density and the current density j refer to the free charge and current densities f and jf of the free electrons, whereas the actual densities tot and jtot also include the contributions from bound electrons. From a macroscopic point of view this can be observed as a (partial) reection, transmission and absorption of radiation. Microscopically an electric eld E (r , t ) leads to a displacement eld D as well as a current j inside a solid: Di (r , t) = ji (r , t) =
i,j

) ( ) r , r , t, t Ej r , t dt dr

(3.5) (3.6)

( ) ( ) i,j r , r , t, t Ej r , t dt dr
i,j

where i and j are the respective components of the elds,

is the dielectric tensor and i,j is

the conductivity tensor, both characterizing the response of the system. For isotropic materials (e.g. cubic lattices) the tensors are reduced to scalar complex numbers and in frequency space we obtain: ( ) =
1 ( )

+ i 2 ( )

(3.7) (3.8)

( ) = 1 ( ) + i2 ( )

3 Theoretical Background All real and imaginary parts of response functions are connected by the Kramers-Kronig relations (here given for conductivity ): 1 2 ( ) 1 ( ) = d 1 1 ( ) 2 ( ) = d (3.9) (3.10)

In this thesis, we will work with thin metal lms: in metals, electron bands are only partially lled and electrons can move in a quasicontinuum of states within the band. For this material class, intraband transitions play an important role in addition to the interband transitions also found in other material classes like semiconductors. The quantity of choice in order to physically describe the response of metals is the complex conductivity: ( ). However, all = n + ik are interchangeable and connected response functions = 1 + i 2 , = 1 + i 2 N through simple equations: 1 = = 2 4 nk 21

(3.11)

2 = (1 1 ) 4 ) ( n2 k 2 = 1 1 4

(3.12)

3.1.1 Drude Model and Extended Drude Model

Classical Drude Model According to the Drude model, electrons in a metal move like particles of a classical free electron gas. In presence of an applied electric eld the electrons are accelerated, but their movement is damped by a factor m/ due to scattering with other particles, which leads to the following equation of motion: mr + m r = eE (3.13)

The parameter 1/ is the scattering rate and an important characteristic of the system. In case of a constant electric eld, a stationary state is achieved when mr = m r eE = 0 (3.14)

With the electron density n and the current density j being connected by j = ner (3.15)

3.1 Interaction of Electromagnetic Radiation with Metals we obtain Ohms law and the expression for the dc conductivity: j = ner 2 ne = E m = dc E ne2 dc = m For a time-varying electric eld of the form E (t) = E0 eit the conductivity becomes ( ) = 1 ( ) + i2 ( ) 1 ne2 = m 1 it dc = 1 it 2 2 p p 1 = +i 4 1 it 4 1 it where p is the plasma frequency with
2 p =

(3.16) (3.17) (3.18) (3.19)

(3.20)

(3.21)

4ne2 . m
2 p 4

(3.22) = 10000 s1 and = 0.1

Fig. 3.1 shows an example of 1 and 2 for the parameters

s. Although the derivation is performed classically, a quantum mechanical calculation of the

1 0.8 0.6 0.4 () [10 cm ]
1

0.2 0 1 0.8 0.6 0.4 0.2 0 1 10 10

0

10 1 [cm ]

10

10

Figure 3.1: frequency dependent conductivity

3 Theoretical Background frequency-dependent conductivity of a non-interacting Fermi gas yields the same results (DrudeSommerfeld model, see e.g. [11]).

Extended Drude Model As shown above, the frequency dependency of the conductivity follows equation 3.21 in a classical Drude analysis. So far the scattering rate = 1/ has been assumed to be a frequency independent, sample- and temperature-dependent constant. Extended Drude theory removes this restriction and describes the consequences of this additional degree of freedom for the optical conductivity. With the extended model one is not limited to systems that can be described with the classical Drude model. ) to be explicitly frequency dependent does not alter the derivation of the optical Taking ( conductivity, the form remains the same: ( ) = 0 = = 1 1 i

ne2 1 1 1 i m

ne2

1 ) i m (

(3.23)

) also has to be As the response function ( ) has to remain Kramers-Kronig consistent, ( Kramers-Kronig consistent and therefore complex. We dene: ) = ( ( ) m ( ) 1 m ( ) +i 1 ( ) m m (3.24)

and insert this expression into eq.(3.23) for the conductivity: ( ) = ne2 m 1
1 m ( ) ( ) m ( ) i mm

(3.25)

); ( ) Here m ( ) and ( ) are real and connected via the Kramers-Kronig relations for ( is the frequency-dependent relaxation time and m ( )/m is the frequency dependent eective mass renormalization factor. It is now possible to calculate a frequency-dependent scattering rate and a frequency-dependent enhancement of the eective mass from measurements of the frequency-dependent complex conductivity. By introducing the eective mass, interactions can be taken into account that were not present in the classical Drude gas of metallic electrons. An extension of the simple Drude model allows us to analyze the optical properties of any kind of material by using the terms introduced in the classical Drude analysis for metals.

3.2 Ferromagnetism

3.2 Ferromagnetism
All the samples investigated in this thesis were ferromagnetic or closely connected to ferromagnetism. Heusler and Permalloy lms are well-known ferromagnets; the Sr1x Cax RuO3 series exhibits a quantum phase transition from a ferromagnetic to a paramagnetic phase. In order to understand the physical properties of these materials, it is crucial to introduce some important concepts for ferromagnetism (see also [12], [13], [14]). We speak of magnetic order if the intrinsic microscopic magnetic moments mi are aligned with one another in a specied way that results in a spontaneous magnetization M=
i

mi

(3.26)

even without an exterior magnetic eld. These systems can take the form of ferro-, antiferro-, or ferrimagnetic order, depending on their microscopic properties. Well known examples for

Ferro

Antiferro

Ferri

Figure 3.2: dierent types of magnetic order. Ferromagnet: parallel magnetic moments; antiferromagnet: antiparallel magnetic moments, magnetizations of the two sublattices cancel each other; ferrimagnet: antiparallel magnetic moments, magnetizations of the two sublattices have dierent absolute values.

ferromagnets are Fe, Co and Ni. An iron bar in zero eld does not necessarily have a non-zero total magnetization M , which is due to the formation of domains: the system saves energy by separating into small regions with uniform magnetizations. Without applied eld, the magnetizations of these domains are not aligned. Ferromagnetic order also competes with entropy: above a certain temperature (Curie temperature TC for ferromagnets and N eel temperature TN for antiferromagnets) every material becomes a conventional paramagnet. The susceptibility of a ferromagnet in the paramagnetic regime above the Curie temperature then follows the Curie-Weiss law: = C T TC (3.27)

The underlying driving force for magnetic ordering is the exchange interaction. For the localized electrons 1 and 2 at positions r 1 and r 2 with the two normalized wave functions a and b ,

3 Theoretical Background the exchange integral J gives a measure for the strength of the interaction: J
3 a (r1 )b (r2 )V (r 1 , r 2 )b (r1 )a (r2 )dr 3 1 dr 2

(3.28)

V (r 1 , r 2 ) represents the potential energy between positions r 1 and r 2 ; J can take positive or negative values: for positive values a parallel orientation of the two spins is energetically favorable, for negative values an antiparallel one. For a system of bound electrons we can write a Hamiltonian including their exchange interaction by taking the sum over all atoms operators i and all neighbors j : H=
i j =i

Jij S i S j

(3.29)

This approach is called Heisenberg model of ferromagnetism. It is valid for e.g. ferromagnetic insulators like CrBr3 , EuO or EuS [12]. Although it is quite descriptive, it is nonlinear and can rarely be calculated. In metallic ferromagnets this concept does not hold anymore if the ferromagnetism originates from the conduction electrons (itinerant ferromagnetism). For these materials a microscopic theory is very dicult to nd, since in addition to the exchange interaction we have to take into account collective electron eects. This theory of band-ferromagnetism was mainly introduced by E.C. Stoner. He used a mean eld approach to derive a feedback mechanism of the Pauli susceptibility of an electron gas. Pauli susceptibility describes the response of an electron gas

E EF
B

B B

DOS
Figure 3.3: energy displacement of the subbands in an external magnetic eld (of downward direction). The dotted line denotes the position of the bands in zero eld. The total magnetization is the net eect produced by the states in the blue region.

to a external magnetic eld. The subband of spins antiparallel to the eld is reduced in energy by B B , while the subband of the parallel spins is enhanced in energy by the same amount. However there has to be one unique Fermi energy in thermal equilibrium, which leads to a higher number of occupied states in the antiparallel subband (g. 3.3). This imbalance results

10

3.2 Ferromagnetism in a total magnetization of the electron gas. The energy shift is very tiny, as B B susceptibility due to Pauli paramagnetism is Pauli = 0 D(EF )2 B (3.30) EF .

With a nearly constant density of states around the Fermi energy, D(E B B ) D(EF ), the

Stoner attributed a positive energy I to each antiparallel pair of electrons. This might seem surprising at rst, but it follows already from the Pauli exclusion principle that a high number of parallel electron spins leads to a lower electron density around the ions, to less screening of the Coulomb interaction between ions and electrons, and nally to an energy gain. We can then consider this exchange interaction and write the energies E (k) and E (k) with respect to the energies of the single particle picture E (k) [13]: n B B n n E (k) = E (k) + I + B B , n E (k) = E (k) + I (3.31) (3.32)

n being the total electron density, n and n being the densities of the electrons with upward and downward spin, respectively. The last term includes the energy shift from the Pauli suscep = E (k) + I/2 tibility due to the magnetic mean eld generated by all other electrons. Taking E (merely an oset to all levels) and the relative up- or downspin excess r = (n n )/n we can write: (k) Ir B B E (k) = E 2 Ir (k) + E (k) = E + B B 2 (3.33) (3.34)

As mentioned above the two subbands have to have a common Fermi energy in thermal equilibrium. Therefore we can write the general relation n=
0

1 D(E )f (E )dE into r = n

D(E ) (f (E (k)) f (E (k)) dE, 2

(3.35)

where D(E ) is the density of states for the total particle density and the factor 1/2 has to be introduced for each of the n and n terms. After inserting eq. 3.34, performing an expansion (E EF ) (for details, see [13]) we obtain around EF and taking f / E r= D(EF ) (Ir + 2B B ) 2n (3.36)

11

3 Theoretical Background Since we can express the total magnetization M in terms of our excess spins r, M = rnB , and the susceptibility is = 0 M/B , the total susceptibility can be written as: = 0 2 Pauli B D (EF ) = 1 [ID(EF )/2n] 1 [ID(EF )/2n] (3.37)

This equation expresses a feedback relation: the higher the value of ID(EF ), the stronger the susceptibility is enhanced. If the Stoner criterion ID(EF )/2n > 1 holds, there is no stable solution and we observe a spontaneous magnetization. The parameter I can be approximated from other parameters like electronic conguration and exchange coupling. Stoners model explains the ferromagnetism of the metallic elements Ni, Co, and Fe well; however, it is very hard to calculate ID(EF )/2n reliably for complicated materials. In a simple physical picture the Stoner parameter I expresses the qualities of band structure, energies, and available electrons with respect to the formation of ferromagnetism. Tiny alterations in one of these parameters through change in the number of charge carriers or changes in the band structure through chemical or mechanical parameters can produce signicant dierences in the magnetic behavior of metals.

3.3 Ferromagnetic Resonance

A ferromagnetic resonance is the ferromagnetic analogue to nuclear magnetic resonance (NMR) or (paramagnetic) electron spin resonance (ESR). In an static exterior magnetic eld H0 , a ferromagnetic material shows enhanced absorption when a high frequency magnetic eld HHF of the resonance frequency is applied. In a quantum mechanical picture, hres is the energy dierence between the two spin states parallel and antiparallel to the eective eld Hef f , which is seen by the sample. In a semiclassical picture, the microscopic magnetic moments precess around the applied eld. Not taking into account damping eects, the equation of motion dM = M He dt (3.38)

describes the undamped precession of the magnetic moment around the eld direction. For H0 z and HHF x the susceptibility x = Mx /Hx in x direction is x = 1 (/res )2 (3.39)

and res depend on saturation magnetization and demagnetization factors of the sample and H0 . Without damping, the susceptibility becomes innity at the resonance frequency. For a physical description we have to introduce a new equation of motion with damping terms, the

12

3.4 Quantum Criticality Landau - Lifshitz - Gilbert equation of motion [14]: ( ) dM = 1 + 2 (M H ) dt |M | ( dM M dt ) (3.40)

with as dimensionless Gilbert damping parameter and = 176 GHz/T as the gyromagnetic ratio, a constant. This is a very accurate form of a magnetic equation of motion, which even includes strong damping. was introduced by Gilbert and can be interpreted as an inverse quality factor of the resonance: = F M R (3.41)

For experiments it is important to see that only an high frequency eld with components perpendicular to the magnetization (e.g. the exterior magnetic eld) can probe a ferromagnetic resonance. From the Gilbert equation it is possible to calculate the frequency dependent permeability ( ) = 1 ( ) + i2 ( ) = 1 + . The real part of the permeability has a zero crossing at the resonance frequency, the imaginary part a maximum [2]. Another zero crossing of the real part is found at higher frequencies: this is the location of the ferromagnetic antiresonance. It does not depend on the perpendicular H0 anymore and should be present in zero magnetic eld. It is possible to retrieve these changes in the complex permeability by measuring the complex impedance ZS , which is connected to the permeability: ZS = RS iXS = i (3.42)

For our experiments we use rectangular 5 mm x 10 mm thin lm samples. As a simple model we take an innite disk in magnetic eld applied parallel to the disk with y disk, H0 and demagnetization factors Nx = Nz = 0 and Ny = 1: 2 fFMR = (M0 + H0 ) H0 (3.43) disk,

3.4 Quantum Criticality

3.4.1 Fermi Liquid Theory
Fermi liquid theory was introduced by Landau in 1956 and denotes a fundamental concept in condensed matter physics, which allows us to treat complex systems with a variety of interactions in a relatively simple manner [8]. Landau found that there is a one-to-one correspondence between the low-energy excitations of a system consisting of non-interacting spin 1/2 particles and the low-energy excitations of a system consisting of interacting spin 1/2 particles. According to the theory, everything can be discussed using terms and context of an independent

13

3 Theoretical Background particle approximation with non-interacting single particles. These particles are actually not the well-known electrons anymore, but quasiparticles with renormalized attributes like an enhanced mass. In a descriptive picture one might think of the quasiparticles as single electrons surrounded by a screening cloud [12]. Main reasons for the applicability of Fermi liquid theory to many metallic compounds are the Pauli exclusion principle and the screening of the Coulomb interaction by other charge carriers. The exclusion principle drastically reduces the scattering rate due to electron-electron interaction because no scattering can take place into occupied energy levels below the Fermi energy. This fact is nicely pointed out by looking at the scattering rate 1/ of an electron of energy E1 near the Fermi surface with energy EF : 1 = a (E1 EF )2 + b (kB T )2 (3.44)

The scattering rate decreases with temperature and proximity of the particle to the Fermi surface. For suciently low temperatures and energy levels not too far from the Fermi energy, the resulting mean free paths are very long and correlated metallic materials can mostly be described by the independent electron approximation. For specic heat and resistivity in a three-dimensional isotropic system at temperatures well below the Fermi temperature, the Fermi liquid scenario yields: C = T = 0 + A T
2

(3.45) (3.46)

As expressed in eq. 3.44, we expect the following low-temperature and low-energy dependence: 1 = b( )2 + a(kB T )2 (3.47)

in which a and b are constant prefactors. As energy scales in orders of kB T in temperature as well as in frequency, this equation also expresses the equivalence of the two dierent energy forms. An important consequence of this equivalence is that both scales have to be low enough to meet the requirements of Fermi liquid theory: optical high energy excitations at lowest temperatures as well as low frequencies at high temperatures usually have to be discussed in a dierent framework. For a normal metal, the expected behavior at low temperatures is that of a Fermi liquid. If a material shows strongly deviating characteristics (in a certain low-energy range), it is considered to be unconventional and therefore interesting. In order to physically understand these materials, a more sophisticated theory has to be developed. Experimentally observed (but not fully understood) disagreement with Fermi liquid theory is simply referred to as nonFermi-liquid behavior. However, it is important to keep in mind that the term non-FL only makes sense if the experiment is performed in a region where FL behavior would actually be

14

3.4 Quantum Criticality expected (e.g. this is not the case for high temperatures).

3.4.2 Quantum Phase Transitions

Quantum phase transitions (QPT) have been extensively studied for the past few decades and are subject of many ongoing theoretical and experimental studies. Even though no actual quantum critical point or quantum phase transition at 0K can be accessed experimentally due to the second law of thermodynamics, the neighboring regions of the phase diagram are highly interesting. QPT are present in many systems that show phenomena like high Tc superconductivity or the quantum Hall eect and are expected to play a signicant role in fully understanding those [15].

Denition and General Aspects As a rst approach to a coherent denition, quantum phase transitions are usually set apart from classical phase transitions (for more details on the following section, see also [16]). Classical phase transitions are driven by thermal uctuations and therefore can only occur at nite temperatures. Their order is determined by the rst discontinuous derivative of a thermodynamic potential. A phase transition from water to ice, for example, involves latent heat (a discontinuity of the heat capacity U/T ) and is of rst order. A phase transition from a ferromagnet to a paramagnet is continuous and of second order. These continuous transitions from an ordered to a disordered phase are described by an order parameter, which is zero in the disordered and non-zero in the ordered phase. For the aforementioned ferromagnetic transition, the order parameter would represent the total magnetization of the system. Although the thermodynamic average of the order parameter is zero in the disordered state, its uctuations can be non-zero and become long-ranged in the vicinity of the critical point, where their typical length scale (correlation length) and typical uctuation decay time scale c (correlation time) diverge: t = ( |T Tc | Tc ) (3.48) (3.49)

c z tz

We call the (correlation length) critical exponent and z the dynamical critical exponent. Critical behavior of nite temperature phase transitions is fully described by classical thermodynamics; quantum mechanics do not play any role even if the actual phases require a quantum mechanical description (e.g. superconductivity) [16]. Talking about quantum phase transitions means talking about transitions at T = 0: by tuning a non-temperature parameter like pressure, chemical composition, or magnetic eld, one could suppress the respective transition temperature like the Curie- or N eel- temperature to 0 K. Ob-

15

3 Theoretical Background viously such a QPT cannot be driven by thermal uctuations; quantum uctuations have to be the underlying source. The terminology used for the description of classical phase transitions in this sections rst paragraph is nevertheless applied. As for a classical second order transition, a quantum second order transition has a quantum critical point (QCP) where the quantum uctuations driving the transition diverge and become scale invariant in space and time. Also at nite temperatures, quantum uctuations with an energy scale of and classical uctuations with an energy scale of kB T compete. For > kB T, quantum uctuations will dominate the systems properties. is the characteristic frequency of a quantum oscillation and inversely proportional to the correlation time. As a consequence it should be possible to detect remnants or traces of the QPT also at low enough nite temperatures: a quantum critical region in proximity of the actual transition or the quantum critical point. These traces become manifest in unconventional and unexpected physical behavior like novel non-Fermi liquid phases. From a theoretical point of view, a phase diagram like the one shown in g. 3.4 is expected: the QPT separates an ordered from a disordered phase (often, the low temperature disordered phase is referred to as quantum disordered). At high enough temperatures, the system is disordered and purely classical. Around the classical phase transition, the system is governed by classical thermal uctuations (light blue area). This region becomes narrower with decreasing energies and converges towards the quantum critical point. Experimentally, the quantum critical phase, which is still governed by quantum uctuations, is the most interesting one.

Figure 3.4: phase diagram of a second order quantum phase transition as expected from theory

Quantum Phase Transitions in Itinerant Ferromagnets Itinerant ferromagnets like SrRuO3 and their phase transitions from an ordered to a disordered state represent a particularly interesting topic: theoretical approaches and their consequences signicantly dier from other ordered systems such as e.g. antiferromagnets. While J.A.Hertz studied this class of antiferro- and ferromagnetic transitions in the 1970s [17] and developed the Ginzburg-Landau-Wilson theory of QPT, recent studies come to dierent and more complex

16

3.4 Quantum Criticality results [10] [9]: due to the coupling of the magnetization to non-critical soft modes in the electronic system, an eective long range interaction between the order parameter uctuations is established. This can dramatically alter the characteristics of the transition, even turn it from continuous second order into a rst order transition. In one possible scenario, the transition would be second order at higher temperatures and turn rst order at some low temperature, marked by the so-called tricritical point. This behavior is experimentally found in MnSi [18]. Another theoretical scenario maintains a continuous transition at all temperatures but changes the ground state from a ferromagnet to a spin density wave. A third possibility would be a conventional second order transition [10]. For the itinerant ferromagnet SrRuO3 , the type of transition has not been determined yet and remains an open question. Similarities with MnSi might indicate the existence of a tricritical point, but so far experiments have not been conclusive. Therefore the order of the quantum phase transition discussed in this thesis still has to be identied. Low-frequency optical measurements at low temperatures are a very appropriate tool to reveal further details of the quantum phase transition in Sr1x Cax RuO3 .

17

4 Measurement Setups and Techniques

4.1 Ranges and Techniques in Optical Spectroscopy
Optical spectroscopy in general is a powerful and frequently used method in condensed matter physics. Frequency dependent response functions of a material, obtained by spectroscopic measurements, provide information on a systems intrinsic properties. Optical observables can be transmission T ( ), reection R( ), absorption A( ), phase shift, polarization, impedance ( ) and other quantities, depending on the measurement technique. The method of choice Z is determined by the energy scale of interest. While many single particle phenomena like e.g. energy scales in band structures are of the order of eV, many interesting phenomena in solids occur at lower energies. In correlated electron systems the interactions of the electrons occur at much lower energies of meV, which typically requires electromagnetic radiation in the far infrared range. An overview of energy scales and observable physical phenomena is given in g. 4.1. For observations of some exotic phenomena even far IR spectroscopy energies are

Figure 4.1: energy scales of some correlated electron phenomena [19]

too high; experiments have to be performed with radiation at even lower frequencies and even longer wavelengths, namely microwave or THz spectroscopy. THz spectroscopy is an optical technique with typical optical accessories. Microwave spectroscopy, on the other hand, diers

19

4 Measurement Setups and Techniques signicantly from optical or quasioptical techniques, as the wavelength exceeds the typical dimensions of experimental setups. Instead of using beamsplitters, mirrors, etc. to guide the electromagnetic wave, coaxial cables, waveguides and directional couplers are needed. The experiments described in this thesis were performed using mainly the two aforementioned methods. Both techniques will be described in detail in the following sections.

4.2 Microwave Measurements

4.2.1 Small Cryostat

Figure 4.2: open continuous ow cryostat with HP 8510C microwave source, test set, network analyzer, temperature controller and multimeter

The so-called small cryostat is a continuous ow cryostat, which was used for microwave experiments in this thesis. It can be operated in transmission and reection mode (description see section 4.2.2) and can be switched from one arrangement to the other in a few hours. Compared to other setups like the microwave spectrometer characterized in [20] or the THz spectrometer that will be described in 4.3.1, it is very small and relatively easy to operate. It consists of two major parts, a coldnger with the helium transfer tube and an aluminum frame. A view of the workplace with all large-scale parts is shown in g. 4.2: the cryostat in the front is connected to the testset by a coaxial cable. The testset obtains its outgoing microwave signal from the source (left in the picture) and transfers it to the vector network analyzer (NWA) HP 8510C. On top of the NWA we nd the temperature controller, and next to the NWA a multimeter that shows the dc resistivity of the total transmission or reection line. Depending on the operation mode, dierent sample holders are used. Fig. 4.3 shows the two types. With our setup we are able to apply a static magnetic eld using permanent magnets with mechanically variable distance between the poles. The eld at the position of the sample

20

4.2 Microwave Measurements

Figure 4.3: sampleholders for broadband microwave transmission (left picture ) and reection (right picture ) measurements. The transmission sample holder has two connectors for two coaxial cables; ths signal ows through the sample, which is located in the middle. Only one coaxial cable goes into the reection sample holder from the back, a spring presses the sample against the contacts from the front side. The small drill holes on the front side are spots for temperature sensors and heaters

can be tuned continuously between 20 mT and 168 mT. All static magnetic elds are applied parallel to the sample, meaning that the magnetic eld lines lie in the plane of the thin lm.

4.2.2 Transmission and Corbino Geometries

This section is dedicated to the description of the two microwave techniques used. Unlike the most common microwave technique we did not use resonant cavities but perform broadband spectroscopy. In our setup the microwave signal was guided through semirigid coaxial cables into the vacuum chamber of the small cryostat, where it was passed onto the sample holder. Two dierent geometries and sample holders were used: Corbino geometry for reection measurements and stripline geometry for transmission measurements. Fig. 4.4 shows the arrangement inside the reection sampleholder. The microwave signal enters the setup through the coaxial cable, the contact of the inner conductor with the sample is established by inserting the center pin. Gold contacts have to be applied onto the sample via vapor deposition prior to the measurement. The inner and outer conductor of the coaxial cable are then pressed against the sample with its contacts by a spring. Thus, the elds of the microwave signal are reected inside the sample and can probe its qualities. The distribution of the magnetic and electric elds of the TEM wave solution in a coaxial transmission line are shown in g. 4.5. Here the transmission line characteristics depend on the geometry of the line, namely the diameters a and b (in particular their ratio). Further reading and mathematical derivations on coaxial cables can be found e.g. in the chapter Transmission Lines and Waveguides of [21]. In reection geometry only one short coaxial cable is needed. The quality of the contact between sample and coaxial cable is accessible through the dc resistance: a sudden rise in resistance can be caused for instance by a displacement due to fast temperature variations and considerably

21

4 Measurement Setups and Techniques

Figure 4.4: schematic view of a Corbino sampleholder as used in the reection experiments [20]

B E
H W E B

Figure 4.5: eld distributions of the TEM mode in a coaxial waveguide (left side) and a strip transmission line (right side)

downgrades the measurement. Consequently, the dc resistance has to be monitored carefully. Fig. 4.6 gives a detailed impression of the transmission stripline arrangement inside the sample holder: the coaxial cables are connected to the microwave striplines by SMA adapters and their tiny pins. It is crucial for the experiment that there is good electric contact between the pins and the transmission line. As in Corbino geometry we continuously monitor this contact by simultaneously measuring the dc resistance of the total transmission line, including test set and coaxial cables. Suciently good contact is achieved if Rdc is approximately 4 . Inside the sample holder the inner conductor is represented by a meander shaped stripline. It is deposited on a Teon dielectric, which separates the stripline from the copper bottom of the sample holder. The actual sample, the thin lm, is separated from the transmission line by a second thin Teon dielectric and serves as ground plane. Electric and magnetic elds propagating through the meander structure probe the respective sample properties. Again, the solution for the propagating wave is a TEM mode. Its eld distribution is outlined in Fig. 4.5. Here the crucial parameters are H and W: the distance between the two ground planes and the width of the transmission line, respectively. Further details are again found in [21]. For transmission measurements two coaxial cables are used. They have to be bent to match the sources and the cryostats dimensions and can make the experiment challenging: the heat input is doubled and the longer transmission lines might introduce additional standing waves or other non-sample-related artifacts.

22

4.2 Microwave Measurements

sample substrate metallic film (sample)

NWA

dielectric optional: metallic edges Teflon MW stripline

pins MW source

Figure 4.6: schematic view of a broadband transmission sample arrangement as used in our experiments

4.2.3 Calibration
For broadband microwave spectroscopy a good calibration is crucial for good measurement results. Concerning the experiments discussed in this thesis, reection measurements require a sophisticated calibration technique. First some information will be given on the calibration procedure for transmission measurements, afterwards the focus will lie on the error model and calibration for Corbino geometry.

Transmission As we will see in this and the next paragraph, transmission measurements are much easier to calibrate than reection measurements. The quantity of interest is the actual transmission T through the device of interest. However, the measured transmission Tmeas does not only record the radiation losses in the sample, but also other losses from connectors and transmission lines. An important error contribution for reection measurements originating in the directional couplers inside the test set is not present for transmission measurements because two separate ports perform the detection of incoming and transmitted signal. Other errors might occur, some signal could reach the detector without interacting with the sample; or some signal could be reected inside the transmission line and interact with the sample more than just one time before reaching the detector. For a reasonably high transmission, however, it is appropriate to neglect these minor errors. Generally it would be sucient to just measure a reference without a sample and normalize the sample spectra to it. This kind of calibration neutralizes the most obvious and signicant error in the setup, namely the damping in the transmission lines. For quantitative high precision measurements, a more sophisticated calibration method should be used in transmission geometry as well (for details see [22]). During the measurements for this thesis calibration was even less of an issue, because the only interest lay in relative changes with an external parameter (in this case applied magnetic eld).

23

4 Measurement Setups and Techniques Therefore it was sucient to normalize all spectra to one particular spectrum (mostly maximum magnetic eld) without performing a real calibration at all. Error Model for Reection In contrast to a transmission setup, reection measurements always require a thorough calibration. Especially the errors produced by directional couplers (the microwave analogue to optical beam splitters) have to be accounted for. These couplers are required for the separation of incoming and outgoing signals, which are measured on the same port. An error model with
MW source ER

ED S 11,m

ES

S11

MW detector, NWA

Figure 4.7: error model scheme for reection microwave measurements. S11 is the real reectivity of the sample, S11,m the measured one

three dierent types of errors is the simplest solution that includes all possible error scenarios of a reection measurement. These three possible errors can be seen in g. 4.7. ED : ES a part of the signal might reach the detector without having interacted with the sample. It will misleadingly increase the reection (directivity) another part of the signal might interact with the sample properly without reaching the detector directly afterwards. Reection along the transmission line will guide it back to the sample and thereby articially increase the incoming radiation from the source (source match) ER like for transmission measurements, the microwave coaxial cables are far from lossless. Attenuation of the signal is represented by a third error factor (reection tracking) Real and measured reection coecients are connected by the following relation [20]: S11,m = ED + ER S11 1 ES S11 (4.1)

From this expression we can isolate the desired quantity, the real reection of the sample: S11 = S11,m ED ER + ES (S11,m ED ) (4.2)

24

4.2 Microwave Measurements By performing a calibration with three standards we will be able to determine the three error coecients. Reection coecients and impedances of the sample and cables are connected by S11 = ZL Z0 ZL + Z 0 (4.3)

Z0 is the characteristic impedance of the coaxial cables, usually 50 . By performing a three standard calibration we set the positions of three dened points in the complex plane. Their locations are often visualized in a Smith chart, a projection of the right half of the complex plane onto a circle. By dening three points, the complex mapping function S11 =
ZL Z0 ZL +Z0

becomes unique and the error coecients are determined. At room temperature it is possible

Figure 4.8: Smith chart with Short, Open and Load locations in the complex plane (empty Smith chart from www.wikipedia.de)

to perform a room-temperature calibration with a well-characterized and precise commercial calibration kit. This calibration, however, is only perfect for devices with appropriate microwave connectors. For our samples, a calibration has to be performed with standards with sampleidentical geometry. Precise measurements at low temperatures require a cryogenic calibration. It determines the exact error coecients for each temperature and takes into account changes in standards, setup parts and coaxial cables. For cryogenic temperatures the standards were fabricated in our department. Our three calibration standards are:

25

4 Measurement Setups and Techniques

Short: ideally it represents a short circuit as termination to the microwave transmission line. Its load-impedance should be ZL = 0; for the complex reection coecient S11,short = 1. As realization of a Short, usually a gold lm is vapor deposited on a piece of bulk aluminum. It should have a DC resistance in the range of R 2 , which corresponds to the coaxial cable resistance. Due to the small absolute resistance it is particularly important that the contact between sample and conductors does not yield any contributions to the resistance and therefore to the calibration. Open: the Open standard is the simulation of an open end. Simply leaving the contacts without any sample should give the same results, but to ensure that the geometry of pin and contacts is the same as for a real sample, a bulk Teon sample with a very high (ideally innite) resistance is measured. Due to test set artefacts, an actual resistance of R 1 M is measured with the multimeter. The reection coecient for an Open is S11,open = 1. Load: for a conventional three standard calibration the load standard should have a dened load impedance ZL matching Z0 = 50 . The reection coecient would be S11,load = 0 like in the shown Smith chart. In fact we do not use a load impedance of 50 , but a NiCr (alloy of 80% Ni and 20% Cr) thin lm with an impedance of ZL 10 . Although it is more challenging regarding data analysis, it has been the best working solution so far. An important fact is that NiCr has an almost temperature independent conductivity. However, fabricating a lm of 50 impedance would require much thinner lms. Using thicknesses below the skin depth might lead to contributions from the substrate; in addition, thinner lms are more dicult to fabricate. Theoretically, this fact does not aect the quality of the calibration at all: any three points in the complex plane dene the mapping. It is only a question of convenient calculations. For samples with resistances close to a Short standard it can be an advantage to have a Load with less than 50 : if the calibration is not perfect (which, in reality, is always the case), the errors will be smaller close to the calibration standards. All microwave measurements were performed with a three standard calibration. There are other ways to perform calibrations for a Corbino geometry [20], which will not be described here.

4.2.4 Data Analysis

From the Corbino reectivity measurements it is possible to obtain the complex frequency dependent impedance and conductivity. How exactly this is done will be the subject of the following paragraphs. Transmission measurements will not be mentioned anymore, as the only data analysis was to normalize the data. For their experimental task the pure transmission spectra were very well suited and satisfying. In principle it should be possible to calculate ( )

26

4.2 Microwave Measurements from the transmission data as well, but a very precise knowledge of all material parameters and geometries would be necessary. Taking equation 4.3 we obtain a relation for the unknown load impedance of our sample: ZL = Z0 1 + S11 1 S11 (4.4)

All samples were metallic thin lms on low-loss dielectric substrates with lm thicknesses between 40 nm and 90 nm. Skin depths for metals in the microwave region being in the range of 1 m, it is valid to assume that the lm thickness is much lower than the skin depth and that substrate contributions can be neglected. For this case the conductivity is connected to the impedance by a simple relation: = ln(b/a) Z 2d (4.5)

a and b being the diameters of inner and outer conductors as shown in g. 4.5 and d the lm thickness. We can therefore summarize microwave reection data analysis with the following scheme:
eq.4.4 eq.4.5 err.corr. 11,m L S S11 Z

(4.6)

Data analysis is done electronically by a specically designed Labview program: the spectra are usually measured using a commercial room temperature calibration of the NWA. Although we will not include this calibration into the analysis process, it is convenient to use it in order to obtain a rst impression of the spectra and identify major errors. Later on, the analysis program extracts the commercial calibration and applies the tting calibration spectra to the sample spectra at each temperature. From the actual reection coecient, the impedance and afterwards the conductivity is calculated.

4.2.5 MW Measurement Accuracy

A detailed description of possible errors in Corbino geometry with a three standard calibration and samples with low impedance can be found in [20]. Although the analysis was done for another spectrometer, the performances should be comparable: even though calibration and measurement procedures are performed in a more elaborate and reproducible way in the big cryostat, the damping in the small cryostat should be lower and the absolute signal higher due to shorter cables. The network analyzers have the same performances and the analysis procedures are exactly the same. In summary it can be concluded that the overall error of the Corbino measurements can reach approximately 10%. Generally, the lower frequencies can be measured with a very high reproducibility and have a much lower error. For most Corbino measurements in this thesis, such a small error of the absolute value of the conductivity is not critical. The measurements are performed to analyze the conductivity in a large frequency range; we are not so much interested in the absolute values rather than in the frequency dependency. Also other

27

4 Measurement Setups and Techniques features like substrate resonances can disturb the analysis of the lm characteristics. Compared to their magnitudes, the spectrometer errors are small. Minimizing these features would be the major goal for the present state of the spectrometer. The microwave transmission measurements were only analyzed with respect to ferromagnetic resonance in a frequency region from 45 MHz to 12 GHz. In this case the precision is given by the noise levels after normalization of two spectra. At least up to 10 GHz, the noise levels are between 0.1 % and 0.3 %. Only in cases with high spectrum-dependent standing waves, the levels rise to 0.5 %. These levels are very low and well suited for small ferromagnetic resonance eects, but it should be noted that we only have to look at normalized raw data without any interest for the absolute conductivity values.

4.3 THz Measurements

4.3.1 THz Spectrometer
In addition to the microwave spectrometer also a THz spectrometer was used. While the microwave source could generate signals in a frequency range of several MHz to over 40 GHz, all THz sources together cover a range from 3 cm1 to around 47 cm1 (90 GHz to 1400 GHz). Radiation in this particular frequency range cannot be generated by only one source for all frequencies. Every source only covers a more or less narrow frequency band. It is therefore advantageous to measure with as many sources as possible to obtain detailed information on the sample spectrum. In g. 4.9, the frequency-dependent power output of the dierent sources is shown. The radiation is monochromatic, linearly polarized and is generated by Backward Wave Oscillators (BWO). In these devices (also called carcinotrons), electrons from a cathode are focused into a beam by a magnetic eld and are accelerated by a high voltage. The beam interacts periodically with an electric eld propagating in a slow-wave structure (e.g. a wave guide with varying diameters and thus a comb-like cross section) in opposite direction (backward). By adjusting the electron beam velocity and phase velocity of the electric eld, the electron beam can transfer energy to the electric eld in the wave guide. Close to the electron gun, the output power is coupled out. The frequency of the output can be continuously tuned in the BWOs frequency range by the applied high voltage. Further reading on theory and application of BWOs and other types of microwave tubes is found e.g. in [21]. Unfortunately BWO sources have a limited lifetime and are subject to wear: not all frequencies shown in 4.9 were accessible during the time of this project. Especially for metallic lms with considerable absorption, the initial power output has to be suciently high. This was not the case for all listed BWOs. The spectrometer itself consists of a Mach-Zehnder interferometer shown in g. 4.10. With this setup it is possible to perform transmission and phase measurements as described in the following two subsections. As detectors we use either a Golay cell or a bolometer. While the Golay cell is very easy to operate and does not need any preparations in

28

4.3 THz Measurements

(mm) (GHz) 0

2 200

0.7 400

0.5 600

0.4 800

0.3 1000

0.25 1200

0.2 1400

OV69

Detected BWO output power (mW)

OV74
OV71

OV24 OV30 OV32 OV80 OV81 OV82 OV84 OV83 OV85

100

OV86

10

0.1

0.01
Water vapor absorption lines

10

20

30
Frequency (cm )
-1

40

50

Figure 4.9: output power of the dierent THz radiation backward oscillator (BWO) sources [23]

advance, the more sensitive bolometer has to be operated at very low sub-4 He temperatures. However, the Golay cell can only be used for sources with high output power. Especially at higher frequencies, the sensitivity of the bolometer is needed for good results. At room temperature the sample can be mounted onto a simple frame with an attached aperture. For other temperatures, the sample is located inside a cryostat. The THz beam has to enter it through windows. Its diameter is reduced to a size suitable to the sample size by an aperture. Fig. 4.11 shows the positions of sample and frame in the sampleholder. The aperture is surrounded by absorbing material and its side facing the beam is coated with an absorbing varnish to prevent reection of the radiation. On the other side a metal frame with a stretched mylar foil and the sample on top can be moved up and down. Usually three dierent positions are specied by circular holes in the mylar: two outer positions for samples and the middle position for the calibration measurement, the empty aperture (g. 4.11). Every spectrum requires two measurements, one reference and one sample measurement. The sample behind the aperture can be switched mechanically from outside the cryostat. For every measurement the entire frequency range of the source is recorded, taking as many points as specied by the user, in our case usually 200 or 300 per spectrum. With this setup samples can be cooled down to temperatures as low as 2 K using liquid 4 He. The cryostat has dierent chambers (see g. 4.12): in the innermost one, the sample with its frame is arranged in a helium exchange gas. Its pressure can be monitored and tuned from outside. A 4 He bath surrounds the sample chamber, while an isolation vacuum chamber thermally disconnects the 4 He bath from a liquid

29

4 Measurement Setups and Techniques

Figure 4.10: interferometer setup used for transmission and phase measurements

a b

Figure 4.11: frame and sampleholder used for THz measurements: picture a shows the side facing the incoming beam, pictures b, c and d show the arrangement of frame, aperture and samples

30

4.3 THz Measurements nitrogen bath. Temperatures down to 5 K are reached without lling the nitrogen bath. For the lowest temperatures we have to continuously pump on the 4 He bath, reducing the pressure. Additional screening from the outside room temperature environment by the liquid nitrogen is needed.

Figure 4.12: diagram showing the dierent chambers of the bath cryostat used for THz measurements (drawing created by the mechanical workshop of the physics department, university of Stuttgart)

4.3.2 THz Transmission Measurements

Transmission measurements only require one arm of the interferometer, the second arm with lenses 5 and 6 has to be blocked. Both Golay cell and bolometer need a modulated signal. In transmission this is achieved by a chopper, which is usually located located between lenses 1 and 2. Typically for thin lms on dielectric substrates, one will obtain an oscillating pattern in the spectra. An example can be seen in g. 4.13, where unprocessed data of four dierent sources are displayed by the THz analysis program. Amplitudes and frequencies of these resonances together with thickness of the sample are used to analyze the data. Transmission through the sample with the metal lm is lower than transmission through the substrate by a factor of 10 (note the logarithmic scale). For lower temperatures as well as for better-conducting lms this factor can increase by several orders of magnitude. The origin of these Fabry-Prot resonances is interference of transmitted and reected radiation; the plane parallel surfaces of the sample act as reectors.

31

4 Measurement Setups and Techniques

NdGaO CaRuO

transmission

0.1

0.01 10 20 30
-1

40

50

frequency (cm )

Figure 4.13: transmission raw data of CaRuO3 on a NdGaO3 substrate of dierent BWOs at 300 K (logarithmic scale)

Transmission through a slab of dielectric

Working with a metallic thin lm on a dielectric substrate means working with a layered system. It is a rather complex task to describe such a system directly. For data analysis the empty substrate is also measured together with the sample and its optical properties are determined. We will therefore discuss a single layer transmission through a dielectric slab rst, mostly following [11]. In contrast to g. 4.14, the beam in our experiment hits the sample at (nearly) right angles. For clarication the angle is not represented as 90 in the picture. The goal is to calculate the resulting reection, transmission and phase change. The underlying principle to this calculation are the Fresnel formulas, which describe transmission and reection at interfaces. In the case of THz measurements with the described setup, the beam travels through a low- to room-pressure He gas atmosphere. We assume
1

= 1, 1 = 1, 1 = 0 in the He gas,

like in vacuum. For normal incidence the Fresnel equations yield the following expressions for the complex reection and transmission coecients of an electromagnetic wave traveling from medium 1 to medium 2: r 12 = 12 = t 1 N 2 N 1 + N 2 N 2 2N 1 + N 2 N (4.7) (4.8)

Using this basic relation for a one-layered system, namely a slab of dielectric, we obtain the 2 following transmittivity T = Stransmitted /Sincident = 1 |t| and phase change of the transmitted

32

4.3 THz Measurements wave t : T = 4n (1 + n)2 + k 2 k n+1 (4.9) (4.10)

tan t =

is the complex transHere 1 is the real part of the dielectric function in the dielectric and t mission coecient, i.e. the ratio of transmitted and incident elds and their phase shift. In this = n + ik in their shortest and clearest form. section all physical quantities are expressed via N As mentioned earlier, it is also possible to express them via or using equations (3.12), but the expressions become much more complicated: )1/2 ) 2 + 2 1/2 + 1 2 2 )1/2 ( )1/2 ( 2 + 2 )1/2 + (1 2 + 2 2 )1/2 + 8 ( 1 2 2 ( 32 )1/2 ((

T = 1+
4

(4.11)

Although we will not actually analyze any data using n and k , this will often be the representation of choice when it comes to mathematical expressions. Taking into account multiple

Figure 4.14: reected and transmitted elds through a slab of dielectric material

reections and transmissions at the two interfaces of a slab of dielectric, we obtain: ( T t = ) (1 RB )2 + 4R sin2 r el
2

(1 RB el ) + 4RB el sin2 ( + r ) 2nl k (n2 + k 2 1) = arctan 2 0 (k + n2 )(2 + n)n RB el sin2 + r + arctan 1 RB el cos2 ( + r )

(4.12)

(4.13)

In these expressions RB , , , 0 and r represent the bulk reectivity of the material, the attenuation of the wave in the material, the phase change of the reected wave, the wavelength

33

4 Measurement Setups and Techniques in vacuum and the phase of the reected wave, respectively: RB = (1 n)2 + k 2 (1 + n)2 + k 2 4k = 0 2nl = 0 2k r = arctan 1 n2 k 2 (4.14) (4.15) (4.16) (4.17)

For intermediate optical thicknesses (nl ) we obtain a series of maxima and minima with a separation of f = c 2nl
2

(4.18) = 0) the transmission at a

between two maxima. Without considering damping eects (

maximum is 1. The above described model usually applies to pure substrate measurements like the red-colored spectra in g. 4.13. Consequently it is possible to calculate the optical constants for the substrate from these spectra. Damping and a weak frequency dependency are taken into account by tting each transmission maximum independently, using the best
2 1

and

values.

Multi-layer transmission While a one-layer model is sucient to describe the substrate, a sample with a thin lm needs a multi-layer model, in this case a two-layer model with three interfaces and four media. 1234 = t 12 t 23 t 34 ei(2 +3 ) t 1+r 12 r 23 e2i2 + r 23 r 34 e2i3 + r 12 r 34 e2i(2 +3 ) i t, 1234 1234 |e = |t (4.19)

In our case medium 1 and 4 are the same, 4 He gas (treated like vacuum). p with p = 1, 2, 3, 4 has been dened as the complex angle i p = p + p lp 2 np + ikp = 2lp 0 (4.20)

It is now possible to determine the optical constants of the lm if its thickness and the substrates optical constants are known. For a small frequency range it is always possible to nd good t parameters. Large-scale frequency dependences of the spectrum might not be accounted for by this model and have to be inserted into the data analysis tool by hand. If the thin lm is metallic and has a high conductivity, it is often more convenient to analyze data in terms of a

34

4.3 THz Measurements local (in terms of frequency) Drude model with DC and damping as t parameters. Especially in cases with very low transmission it is recommendable to analyze only a small frequency region around the transmission maximum. The signal to noise ratio is much higher there than in the low-transmission regions and should lead to more precise results.

4.3.3 THz Phase Measurements

The ability to perform phase measurements sets frequency-domain THz spectroscopy apart from many other spectroscopic techniques like, e.g., Fourier transform infrared spectroscopy. No data extrapolation for an otherwise frequently used Kramers-Kronig analysis is required. Measuring the phase shift, which is caused by the sample, requires a reference arm to interfere with the sample arm. For that purpose we use a Mach-Zehnder interferometer as shown in g. 4.15. The polarizations of the dierent beams are crucial to the experiment and also indicated in the picture. All beam splitters in the interferometer are gratings which reect one light polarization and transmit the other fraction. BWO sources emit nearly perfectly polarized light. The polarization can be tuned by the rst polarizer. The beam is changed to a polarization of 45 , so that at the rst beam splitter half of it is reected and the other half is transmitted. As a consequence, radiation in the second arm has a perpendicular orientation compared to radiation in the rst arm. The two arms of the beam are overlapped by the second beam splitter, but they can not yet simply interfere with each other, because the polarizations are orthogonal. Only after their polarizations are changed to 45 by the analyzer, well-dened interference minima and maxima (depending on mirror position) become visible. Success and accuracy of phase measurements highly depend on the alignment of the interferometer. While beam splitters and mirrors are in principle only aligned once, namely when the spectrometer is set up, all lenses have to be readjusted every time a new BWO is used. To align the lenses the second arm is blocked and the lenses are positioned one after another (rst lens 1, then 6, 2 and 3), always trying to maximize the signal. Then the rst arm is blocked and lenses 4 and 5 are aligned in the same manner. The quality of the alignment can be checked by opening both arms and moving a mirror from interference minimum to maximum. The higher the ratio signalmax /signalmin , the better the alignment. Another dierence compared to transmission measurements is the modulation of the signal: it is not done by the chopper but by an oscillation of the second mirror. During a phase measurement, the movable mirror in the second arm is electronically kept at the position of the interferometric minimum. It is therefore important to determine the 0th order, where the optical paths of the two arms are exactly the same, as starting position. This order is characterized by its frequency independence. A subroutine of the measurement program is able to determine the 0th order. For high frequencies the wavelength becomes smaller and two interferometric orders are very close. In this case it might be necessary to adjust the position to 0th order manually. Similarly to transmission measurements, a phase spectrum requires two measurements: for each frequency the position of the mirror at the minimum is recorded with

35

4 Measurement Setups and Techniques

Figure 4.15: polarizations of the E vector in dierent interferometer sections (red arrows) [23]

and without the sample. From the dierence between these two positions, the phase shift due to the presence of the sample can be calculated. If xsam and xref are the positions of the movable mirror with and without the sample, respectively, and l is the thickness of the sample, the phase shift is = 2 (xsam xref + l) with in cm1 , all lengths in cm and in radians. (4.21)

4.3.4 Data Analysis

Many mathematical aspects of the data analysis have already been explained in the preceding sections. In this subsection I will only give a summarizing overview on the dierent analysis steps. The data sets obtained with the THz frequency domain spectrometer contain the frequency-dependent transmission at dierent temperatures and, if possible, the frequencydependent phase at the same frequencies. Especially when moving to higher frequencies, phase measurements become increasingly dicult. With some samples, phase measurements might even turn out to be unfeasible. In principle one could simply combine transmission and phase of the lm at every frequency and calculate the conductivity. Another data analysis routine has been established for this spectrometer: transmission data is taken and an appropriate model is applied. For metallic lms, the spectra can locally be described by a Drude term with two parameters, namely dc conductivity and damping (scattering rate/2 ). The dielectric parameters
1

and

of the substrate for the investigated frequency and temperature have to be known and
1

inserted into the substrate parameters. They are obtained by tting every Fabry-P erot maximum of the substrate transmission spectrum with a model for a simple dielectric slab. and
2

of the substrate should remain xed during the tting procedure, but might be slightly varied

36

4.3 THz Measurements beforehand in a reasonable error range of the measured values, if necessary. After that every transmission maximum is tted by varying the two Drude parameters. In case of an automated t, an appropriate frequency range must be chosen, usually one Fabry-P erot oscillation from minimum to minimum. The phase measurement takes the role of an important control parameter: the best t to the transmission should yield a calculated phase curve that ts best to the measured one. Usually this is the case, otherwise the validity of the measurement has to be veried. An even more precise method would be to t phase and transmission simultaneously. This was always done by hand before applying the automated tting procedure, which usually improved the result. Automated simultaneous ts are dicult to perform and usually do not work due to osets in the phase. Every phase measurement is object to mirror and sometimes order correction. Nevertheless, most phase measurements suer from a slight oset. The main advantage of this analysis method compared to others is that it can be performed even if the phase is not available (with some loss in precision, of course). Another positive aspect is that obvious phase osets can be taken into account. A purely mathematical calculation would have to take the absolute phases as measured. A striking disadvantage is the number of data points: while the applied method averages over one oscillation to obtain one point for each 1 and 2 , a point-by-point method would yield a continuous curve with just as many points as the originally measured curve. In summary, the used data analysis formalism looks the following: it starts with the transmission spectrum of the sample. With knowledge about the type of the sample (e.g. metallic, dielectric), an appropriate model with the respective t parameters is chosen. Into that model, the optical properties of the substrate (obtained from a transmission spectrum of the substrate at the same temperature) are inserted as constant parameters. A frequency range, usually transmission minimum to minimum, is specied for the automated t, which eventually returns the t values of the used model (for our Drude model: dc conductivity and damping). Fig. 4.16 shows a graphical scheme of this analysis procedure.
Substr Tr model insert

sample

Tr

1, 2

dc , damping =

trange

4.3.5 THz Measurement Accuracy

Although the error of the spectrometer is known to have an accuracy in the region of 1% to 2%, there are always other factors, which also contribute to the total error. A general quantitative statement on the overall accuracy of the THz results is therefore very dicult to make. Nevertheless, it is important to know the dierent error sources and their impact on the measurements in order to estimate the accuracy of the data. The above mentioned values of 1% and 2% are only valid if all other factors are at least in an average quality range: if the signal

37

4 Measurement Setups and Techniques

Figure 4.16: scheme of the THz data analysis procedure

is weak or if the phase cannot be measured, the errors are considerably higher, up to a range of 10% - 15%. Since we work with metallic thin lms, the transmission is usually low ( 10%) and gets much weaker at lower temperatures due to enhanced conductivity. For the data this means that high conductivity data always has larger errors than low conductivity data. Another aspect is the success of the phase measurement: At our highest frequencies, a phase measurement was not possible for most samples. Without a phase measurement, the error of the damping parameter is larger. The phase is particularly sensitive to the damping parameter, while only large changes in aect the transmission. For our data we have to conclude that the highest THz frequencies have larger errors than lower frequencies. Another aspect is the tting procedure. Sometimes, the t range has an impact on the results of the parameters. This is not always the case, it seems to depend on the specic shape of the maximum and the range of the t parameters. The lowest maximum usually displays standing waves (due to the dimensions of our setup parts), which disturb the t; also the high frequencies seemed to display this problem more often than the other data. In summary, our measurement has the highest precision of 1% or 2% for the substrate measurements, probably a maximum error of up to 3% - 4% including the t errors. The processed conductivity data includes this substrate-error and the error from a lower signal and more complex t procedures. For highest frequencies and conductivities, an error as high as 20% is possible. For low conductivities and intermediate frequencies we are able to obtain lower errors below 10%.

38

5 Samples
The data presented later in this thesis was obtained from several dierent samples on dierent substrates. Sample quality and properties naturally play an important role in the measurements. All these samples were fabricated by collaborating researchers at several facilities. It is therefore convenient to give an overview on sample characteristics and preparation techniques. Although some information will be provided for every sample, the focus will lie on the Sr1x Cax RuO3 doping series and its physical properties.

5.1 Permalloy
Permalloy, the alloy Ni80 Fe20 , was merely used as a reference sample for the Heusler CCFA lm. Its magnetic properties are well known and the occurrence of a ferromagnetic resonance in our accessible frequency region made it well suited to test the setup. Commercially available permalloy wire was evaporated and deposited onto a GaAs substrate by electron beam deposition [24]. Our thin lms samples have a thickness of 50 nm and were provided by Fabian Giesen and Dirk Grundler.

5.2 Heusler
Heusler compounds have recently become a highly studied topic in solid state research. Although rst Heusler alloys with a chemical structure X2 YZ were accessible over a century ago, the most intriguing characteristics and potential applications were only recognized during the past few years. Some have even been proven to be topological insulators [25], realizations of the new concept introduced in 2006 [26]. Members of this large material class are promising candidates for applications in spintronics, as these intermetallic ferromagnets exhibit perfect spin polarization at the Fermi level [27]. In order to benet from their qualities, it is crucial to thoroughly understand the magnetic properties of these materials. Epitaxially grown Co2 Cr0.6 Fe0.4 Al thin lms were fabricated by the group of Martin Jourdan in Mainz [28]. They were deposited onto a MgO substrate with a 20 nm thin Cr buer layer (which enhances the quality of the lm). The Cr layer was deposited by an electron beam evaporator, the actual Heusler thin lm had a thickness of 40 nm and was deposited by magnetron sputtering at a presssure of 108 mbar [28].

39

5 Samples

Figure 5.1: crystal structure of Heusler alloy Co2 CrAl[29] and layered structure of Heusler samples CCFA429 and CCFA430 [28]

5.3 Sr1x Cax RuO3 Series

SrRuO3 and CaRuO3 are important examples of 4d transition metal compounds; their properties are well summarized in [30]. Some of the main aspects will be outlined in this section: they are isoelectronic and both have a distorted perovskite structure. Due to the smaller ionic radius of Ca2+ , the lattice distortion increases with Ca content. Many interesting magnetic and electronic properties are believed to originate in the hybridization between the Ru(4d) and the O(2p) shells and in strong correlations between the electrons within the narrow Ru(4d) band. While SrRuO3 shows ferromagnetic order below TC = 165 K, CaRuO3 is paramagnetic down to low temperatures, although their electronic and structural properties are quite similar. The reason for this signicant dierence has to be the higher lattice distortion, which leads to a slight change in the band structure and the complete suppression of ferromagnetic order [33]. At the crossover between ferro- and paramagnetic systems, Sr1x Cax RuO3 undergoes a quantum phase transition at 70% Ca content. Unconventional physical behavior and possible new phases are expected in this region at low temperatures. We studied thin lm samples of dierent Ca content by probing their properties optically. The Sr1x Cax RuO3 lms were grown at the Georg-August-University in G ottingen by Melanie Schneider by metalorganic aerosol deposition (MAD). This method was mainly developed by V. Moshnyaga and is described in [32]. For this technique, no elaborate vacuum chamber or any high precision instruments are necessary. The lm is simply deposited onto a heated substrate in a conventional air atmosphere. For that purpose a solution containing all desired ingredients except oxygen is mixed with gas (usually nitrogen) in a pneumatic nozzle. The resulting aerosol is sprayed onto the substrate from a certain distance. A chemical reaction is activated

40

5.3 Sr1x Cax RuO3 Series

Figure 5.2: left side: distorted perovskite structure of SrRuO3 and CaRuO3 consisting of RuO6 octahedra and Sr or Ca ions [31]. Ru atoms: purple, O atoms: red, Ca or Sr atoms: yellow right side: metalorganic aerosol deposition scheme [32]

in very close proximity to the substrate, where the aerosol droplets are evaporated due to the high substrate temperature. Oxygen is always available in the surrounding atmosphere and leads to the deposition of a thin metaloxide lm onto the substrate. MAD is very fast, much less precarious than other preparation methods and produces smooth samples with comparably high residual resistivity ratios (T 0)/(300 K) (RRR). Considering the technical simplicity of MAD, the resulting thin lm quality is impressive. Sample quality is signicantly inuenced by the lattice mismatch m between the lattice constants dS and dF of substrate and lm. m= dF dS dF (5.1)

A higher lattice mismatch will typically lead to a lower RRR and a poorer sample quality. Doped samples will mostly have much lower RRR values than pure CaRuO3 or SrRuO3 due to disorder introduced into the system. A detailed documentation on these issues is found in [3]. In summary we measured eight samples on three dierent substrates. Lattice mismatches of the pure compounds can be looked up in the corresponding table (data from [3]): MgO SrRuO3 CaRuO3 6.79 % 8.85% SrTiO3 0.74% 2.08% NdGaO3 1.9% -0.5%

First samples were grown on SrTiO3 and MgO, both very common substrates. While SrTiO3 is superior concerning the lattice mismatch, it has a striking disadvantage for our optical measurements: being a ferroelectric, its optical constants
1

and

are very large and show a strong

41

5 Samples temperature dependence. This leads to strong and temperature dependent substrate-related features in the spectra. Subtracting substrate contributions and analyzing small eects of the thin lm become very hard. For this reason, MgO was initially preferred as substrate despite the large lattice mismatch for our sample lms. NdGaO3 provided a solution to this problem: it is a simple dielectric with reasonable optical constants and has a small lattice mismatch for both SrRuO3 and CaRuO3 . The nomalized dc resistivity curves of the samples on NdGaO3

1.0

0.8

R(T)/R(290K)

0.6

0.4

SrRuO
0.2

Sr Sr

0.6

Ca Ca

0.4

RuO RuO

0.2

0.8

CaRuO
0.0 0 100 200

Temperature (K)

Figure 5.3: temperature-dependent dc resistivity of the four high quality samples on NdGaO3 (data: courtesy of M. Schneider)

are shown in g. 5.3: SrRuO3 (black curve) and CaRuO3 (blue curve) have considerably lower resistivities than the two doped samples at lowest temperatures. CaRuO3 has the lowest lattice mismatch and consequently the best RRR value ( 26, RRR of SrRuO3 14). Highest residual resistivity is found in the doped sample with 40% doping, which is close to the maximum possible disorder of 50% doping. Ferromagnetic ordering results in a change of slope of the temperature dependent resistivity. A clear kink in the black curve denotes the Curie temperature of SrRuO3 at 155 K. Also the red curve of the 40% doping obviously changes its slope rather discontinuously at around 70 K. The other curves do not show such a sudden change in slope, which indicates a lack of magnetic order.

42

6 FMR: Results and Discussion

6.1 Reference Measurements and Permalloy
The main objective for the FMR measurements was nding the FMR in SrRuO3 . An apparently exotic resonance at around 250 GHz was reported for SrRuO3 in a magneto-optical Kerr eect study [1]. Being two orders of magnitude higher than conventional FMR it raised the question if this resonance really was the FMR. On the other hand, no conventional FMR has been successfully measured in that material. With the small cryostat and the broadband microwave signal we work in the region of a suspected conventional FMR and therefore we should principally be able to see it. First we had to test our setup with a well known FMR, but also the empty setup and a nonmagnetic samples to exclude falsely positive results. Fig. 6.1 shows that there is no magnetic
148mT 130mT 1.008 115mT 103mT 92mT
1.002

148mT 130mT 115mT 103mT 92mT

)/Trans(H)

)/Trans(H)

82mT 1.004 74mT 67mT 60mT 55mT 1.000 35mT 24mT

1.000

82mT 74mT 67mT 60mT 55mT

max

max

Trans(H

Trans(H

0.998

35mT 24mT 18mT

0.996

0.996

0.992

0.994

10

12

10

12

frequency (GHz)

frequency (GHz)

Figure 6.1: empty setup and NiCr transmission measurements, normalized to maximum magnetic eld

eld-dependency above the noise level for frequencies below 9 GHz. Above 9 GHz, empty setup and NiCr show magnetic eld dependent resonances. Therefore we should be able to reliably detect FMR at least in the region from 0 GHz to 9 GHz. The next step was to prove the ability of our setup to detect and resolve FMR: Permalloy, Fe80 Al20 , was chosen as reference sample since its magnetic properties are well known. Measurements of the FMR and further information on Permalloy can e.g. be found in [24]. We therefore expected to see the FMR with both our microwave techniques. Transmission measurements are shown in gure 6.2. Raw data had to be normalized to either one particular (here the maximum) eld or to the respective neighboring eld. Otherwise the eect would not

43

6 FMR: Results and Discussion be recognizeable. There clearly is a frequency shift of the resonance with the applied magnetic

1.010

0mT 18mT 24mT 35mT 60mT

1.02

0mT 18mT 24mT 35mT 55mT

1.00

0.98

)/Trans(H)

1.005

67mT 74mT

0.96

60mT 67mT

92mT 103mT 1.000 115mT 130mT 148mT

)/Re(Z)

82mT

0.94

74mT 82mT

0.92

92mT 103mT

max

maxfield

Trans(H

0.90

115mT 130mT

Re(Z

0.88

148mT

0.995

0.86

0.84

0.82

0.990 0 1 2 3 4 5 6 7 8 9 10 11 12

0.80 0 2 4 6 8 10 12 14

frequency (GHz)

frequency (GHz)

Figure 6.2: transmission (left side) and reection (right side) measurements of the Permalloy sample, normalized to the maximum eld data

eld. The order of the resonances can be followed by comparing the colors and is consistent with the change in magnetic eld: there is a one-to-one correspondence of elds and resonances. Another visualization is shown in gure 6.3, a three-dimensional surface plot of all recorded spectra. Red arrows indicate the magnetic eld dependence of the resonance, the FMR path. Dashed arrows show the approximate extrapolation down to zero eld, where the resonance should disappear. Looking at the two shown gures, another aspect is worth mentioning: the best results are obtained if the normalization of the curves works very well. Ideally, normalized spectra should be straight lines with just the resonance at the respective frequency. Also the non-FMR-path area in the surface plot should be at. Other resonances like the ones at higher frequencies disturb the measurement; small changes like the FMR on top of these prominent features might not be detectable at all. It is therefore very desirable to minimize such inuences, may they be related to cryostat, setup, or cables. To summarize the Permalloy measurements we can say that it is denitely possible to measure FMR with this setup in transmission geometry. The eect is small but it can clearly be identied. Reection measurements on the other hand could not be applied yet to nd the FMR. Although most experiences with the new small cryostat were made in reection and although the setup works more smoothly and reliably there than in transmission, FMR could not be detected. Fig. 6.2 shows both the transmission measurement and the corresponding image in reection. All spectra were normalized to the one with maximum eld, the eld strengths are the same as in transmission. We see a quite strong dependence on magnetic eld in the reection measurement, but without any frequency shift with applied eld strength. After looking at transmission data of g. 6.2 we would expect some resonance changing from 4 GHz to around 10 GHz for the applied eld range. It remains unclear why the FMR could not be detected in reection. The relative position of high frequency and static magnetic eld is more advanta-

44

6.2 Heusler Compound

tr (H)/tr (lower H)

1.05 1 0.95 12 10 8 6 100 4 frequency (GHz) 2 0 20 0 60 40 H (mT)

||

140 120 80

Figure 6.3: surface plot of the Permalloy FMR data

geous in transmission as most components of the high frequency eld are perpendicular with respect to the magnetization of the sample. In reection, the magnetic eld travels through the cable in a circularly shaped cross section as shown in g. 4.5. If we assume a circularly shaped eld also in the metallic thin lm, there would be only a few components perpendicular to its magnetization. The measurable eect would be reduced. Taking into account that also in transmission the relative signal is only about 0.5 %, the FMR might be too weak to resolve. Nevertheless, strong FMR has been detected and measured well in Corbino geometry [2]. The essential dierence from our experiment are the samples: in [2], single crystals with a higher impedance were used in contrast to our thin lms. Another issue might be that the reection setup seems more susceptible to variations in magnetic eld even without a magnetic sample: small resonances might be completely covered by the strong features of the reection spectra in g. 6.2. Thus, the complete absence of any FMR trace in reection is not entirely understood and might be (partly) related to several of the mentioned issues.

6.2 Heusler Compound

We performed magnetic eld dependent microwave measurements on the ferromagnetic Heusler compound Co2 Cr0.6 Fe0.4 Al at dierent temperatures. It is a ferromagnetic material with a Curie temperature of 700 to 800K, depending on sample specications [34] and therefore well suitable for magnetoelectronic devices. With FMR studies, magnetization and magnetic moments of ferromagnets can be probed and studied in detail. The epitaxial thin lms were grown on an MgO (100) substrate at room temperature using an rf-sputtering technique described in detail in [35]. A characterization of the magnetic properties of the MgO / Cr(20nm) / Co2 Cr0.6 Fe0.4 Al(40nm) / Al(3nm) samples can be found in [36]. Previously, FMR data had been obtained from res-

45

6 FMR: Results and Discussion onant microwave cavities [37]; we were able to add broadband microwave data at frequencies ranging from 0 GHz to 12 GHz. Technically, the measurable frequency range reaches from 45 MHz to around 40 GHz, but as our interest lies in analyzing a FMR at low magnetic elds, only the relevant low frequency data up to 12 GHz will be used in this section. Since the signal mainly travels along the meander lines and perpendicular to the incoming signal, its magnetic eld will be in the plane of the ferromagnetic thin lm (see g. 4.6). The direction of the magnetic eld lines is perpendicular to the static applied eld and therefore well suitable for FMR studies. Fig. 6.4 shows transmission spectra of a CCFA sample measured at three dierent magnetic elds. The highest, an intermediate and a low eld are cited as examples. From this perspective, dierences between the respective curves are hardly discernible. On the one hand this is a sign of general reproducibility: no temperature uctuation or time dependence aect the spectra, also the magnetic eld dependence of the sample is weak for these elds. On the other hand further processing is necessary for smaller eects. Even a close view on the raw data in the FMR resonance range as shown in the inset of 6.4 does not reveal a signicant magnetic eld dependence. Processed transmission spectra at dierent magnetic elds and a

5
3.0

2.8

2.6

2.4

transmission

2.2

2.0 5

maximum field intermediate field low field

0 0 2 4 6 8 10 12

frequency (GHz)

Figure 6.4: CCFA transmission spectra as measured prior to normalization and analysis. As examples, the maximum (160 mT), one intermediate (70 mT) and one low (25 mT) magnetic eld was plotted. Inset: Detail of unprocessed spectra in proximity of the FMR resonance region, 5 GHz - 8 GHz

temperature of 200 K are shown in g. 6.5. In order to clearly identify the quite small eect of only about 0.5 %, the raw data transmission spectra were normalized to the maximum applied magnetic eld. Up to 4 GHz the normalized spectra show nearly no eld dependence and add up to a quite smooth 100 % line. From 4 GHz to 9 GHz each spectrum shows one maximum at a specic frequency. Above 9 GHz spectra become more dependent on the magnetic eld, but only regarding amplitude. Frequency range and frequency shift of the absorption resonances in the 4 GHz to 9 GHz range show that the origin of the recorded feature is a FMR of the Heusler thin lm. From Lorentian ts of the resonances it is possible to obtain the damping parameter

46

6.2 Heusler Compound

1.010

0mT 18mT

10 9 8 7 frequency [GHz] 6 5 4 3 2 1 0 20 40 60 80 100 H|| [mT] 120 140

1.012 1.01 1.008 1.006 1.004 1.002 1 0.998 0.996 0.994 0.992

1.008

24mT 35mT

1.006

55mT 60mT

)/trans(H)

1.004

67mT 75mT

1.002

82mT 92mT

Max

1.000

103mT 115mT

trans(H

0.998

130mT 148mT

0.996

0.994

0.992

0.990 0 1 2 3 4 5 6 7 8 9 10 11 12

frequency (GHz)

Figure 6.5: left side: transmission spectra normalized to maximum magnetic eld at 200 K right side: grayscale plot; the used spectra were measured at 200 K and normalized to maximum magnetic eld

from F M R = F M R [2]. The damping value of the data in g 6.5 is = 0.097 0.037. It is in a reasonable range for such an FMR experiment, although also much lower values below 0.01 have been reported for Heusler alloys [41]. Similar sets of spectra are obtained for 300 K, 250 K and 150 K with slightly shifted resonance frequencies for the respective magnetic elds. Although the spectra show a clear frequency-dependent resonance, it was very hard to remove

Figure 6.6: 3D surface plot of room temperature transmission spectra normalized to the next higher magnetic eld

background resonances at room temperature. As shown in g. 6.6, the three-dimensional surface plot is less clear concerning the course of the FMR than the analogous plot for Permalloy. The fact that the eect is small compared to any background uctuations remains a problem. By showing a grayscale plot the visual information can be reduced to the region of interest: instead of 14 dierent magnetic elds like in the left picture of g. 6.5, an increased number

47

6 FMR: Results and Discussion of 26 have been measured and included into the datagrid of the grayscale plot. Bright areas indicate the location of the resonant frequency at a certain magnetic eld. At lowest measured elds the resonance frequency is around 4 GHz whereas for higher elds it saturates somewhere between 8 GHz and 9 GHz. As FMR frequencies also depend on temperature, studies at dierent temperatures are desired. We observed broadband FMR at dierent temperatures. In g. 6.7 the FMR frequencies at dierent magnetic elds are shown for temperatures 300 K, 250 K, 200 K, 150 K. The resonance frequencies of the innite-disk-model are also inserted into the plots. For their calculation, the saturation magnetization values 0.609 T, 0.618 T, 0.628 T and 0.635 T from [38] are taken for the temperatures 300 K, 250 K, 200 K and 150 K, respectively. For 150 mT, results are shown in table 6.1. As temperature decreases, FMR frequency and

10
resonance frequency (GHz) resonance frequency (GHz)

10
150 K

9 8 7 6 5 4 3

9 8 7 6 5 4

200 K

20

40

60

80

100

120

140

160

20

40

60

80

100

120

140

160

static field H (mT) 0

static field H (mT) 0

10
resonance frequency (GHz) resonance frequency (GHz)

10
250 K

9 8 7 6 5 4 3

9 8 7 6 5 4

300 K

20

40

60

80

100

120

140

160

20

40

60

80

100

120

140

160

static fieldH (mT) 0

static field H (mT) 0

Figure 6.7: black points and curves: dependence of the FMR frequency on static magnetic eld at temperatures of 150 K, 200 K, 250 K and 300 K; blue squares: resonance frequencies, calculated from eq. 3.43 and saturation magnetization values from [38]

magnetization slowly increase. Magnetization ratios obtained from our broadband microwave measurements with eq. 3.43 can be compared to SQUID data on the same compounds [36] (table 6.8). According to equation 3.43 we expect an increase of the resonance frequency with the applied magnetic eld and the static magnetization corresponding to the blue squares. We clearly see an increase and a qualitatively similar behavior in our data. Quantitatively, the

48

6.2 Heusler Compound Temperature 300 K 250 K 200 K 150 K fFMR,150mT 8.30 GHz 8.72 GHz 8.73 GHz 9.21 GHz M0 0.435 T 0.495 T 0.497 T 0.571 T

Table 6.1: static magnetizations at 150 mT

measurements deviate from the calculations. Especially at low static elds, the measured resonance frequency is too high. At high elds it seems to level o prematurely. One possible reason could be that this simplied model is only valid for a saturated magnetization. Demagnetization values cannot be assumed to be just 0 or 1 for elds in the hysteresis region. Although the magnetization should be saturated already below 20 mT according to [38], also higher values have been reported [40]. Furthermore, the magnetization measurements in [38] were performed on samples of the same fabrication method like the ones used in this work, but with Fe as buer layer instead of Cr. This could also inuence the magnetic properties. Our higher magnetic elds should denitely be in the saturated region. It is however possible that the model explained in section 3.3 cannot be applied quantitatively to the lower magnetic elds. The highest resonance frequencies could be less accurate than the low and intermediate frequencies, because they are located on top of a strong substrate resonance. Another issue are magnetic setup parts (connectors, parts of the sample holder, ...); they could inuence the eective magnetic eld at the location of the sample and therefore the resonance frequency.

M300 / M150 M250 / M150 M200 / M150

MW 0.762 0.867 0.870

SQUID 0.716 0.828 0.914

Figure 6.8: CCFA SQUID magnetization measurements published in [36] and magnetization ratios calculated from microwave measurements. The samples CCFA 429 and CCFA 430 correspond to the black curve in the diagram

49

6 FMR: Results and Discussion

6.3 SrRuO3
One of the main goals of the FMR measurements was to prove the existence or absence of a ferromagnetic resonance in the microwave region for SrRuO3 . Such a result could verify the existence of the reported FMR at a frequency of 250 GHz [1]. This FMR frequency would indeed be very exotic and unexpected: ferromagnetic resonances have not been known to occur at such high frequencies. For SrRuO3 we would expect a resonance at some few GHz for our magnetic eld range (like observed in the Permalloy and Heusler ferromagnets). As for

1.08

148mT 130mT 115mT

1.04

1.03
0mT 18mT

)/corr. refl. (B)

1.06

103mT 92mT
1.02

24mT 35mT

1.04

55mT 35mT

)/trans(B)

1.01

55mT 60mT 67mT

1.02

max

max

1.00

74mT 82mT 92mT

corr. refl. (B

trans(B

1.00

0.99

103mT 115mT

0.98

0.98

130mT 148mT

0.96
0.97

0.94
0.96

10

20

30

40

10

20

30

40

50

frequency (GHz)

frequency (GHz)

Figure 6.9: left side: magnetic eld dependent reection measurements of SrRuO3 on MgO at 70 K. The corrected reection coecient S22 was normalized to the spectrum of maximum magnetic eld. right side: magnetic eld dependent transmission measurements of SrRuO3 on MgO at 70 K. Like for the other materials, all transmission spectra were normalized to the spectrum of maximum magnetic eld.

the other materials, reection geometry was tried out rst. The left side of g. 6.9 shows the processed data. No striking eld dependences are visible except the sometimes more and sometimes less pronounced standing waves. However, reection measurements cannot give a conclusive answer to our problem; as a resonance could not even be detected in the reference sample Permalloy, transmission geometry had to be tried out as well. In contrast to the distinct results for Permalloy and CCFA, no trace of a possible ferromagnetic resonance could be found. The spectra in the right picture of g. 6.9 show some eld dependent small resonances, but none of them change with frequency. All shown spectra were measured at a temperature of 70 K, well inside the ferromagnetic phase of SrRuO3 . Also other temperatures showed no signicant dierences and therefore will not be included into this discussion. Even the spectra well above the Curie temperature of 165 K look very similar to g. 6.9. According to our microwave reection and transmission measurements in magnetic eld, there is no FMR in SrRuO3 in this frequency range. This result is in agreement with the optical Kerr measurements of [1]: if the FMR really occurs at much higher frequencies (for yet unknown

50

6.3 SrRuO3 physical reasons), it will not be possible to detect an FMR in the microwave region. However, such a lack of any physical eect is less conclusive than a positive identication. An FMR might still be present in SrRuO3 in the analyzed frequency range, but very hard to detect. Already in the other ferromagnetic thin lms the eect is quite small. It might be covered by larger eects or substrate contributions. A very broad but weak resonance would be very hard to detect because the normalization would have to be nearly perfect over a large enough frequency range. Some inner stainless steel parts of the setup turned out to be (weakly) magnetic. They could induce changes in the spectra or simply cover weak sample-originated eects. Sample quality probably remains the most important issue: the only available samples during the measurement at the small cryostat were SrRuO3 on SrTiO3 and SrRuO3 on MgO. Samples on NdGaO3 were only fabricated at a much later point and should be studied with microwave spectroscopy in the future. Due to the strong substrate contributions, which we will see in the next section 7.1, the only reasonable option was to measure SrRuO3 on MgO. Unfortunately the lm quality of the sample is comparatively poor (details see section 5.3), with an RRR of only 0.9. As the ferromagnetism is itinerant, strongly enhanced scattering processes in the conduction electrons might aect the magnetization and therefore the FMR.

51

7 Sr1xCaxRuO3: Results and Discussion

7.1 Microwave Spectrometer Results
During the microwave measurements at the small cryostat, three samples of the Sr1x Cax RuO3 doping series were available: SrRuO3 and CaRuO3 on SrTiO3 and SrRuO3 on MgO. Measurements on these samples will be presented in the next two subsections. Fig. 7.1 is a visualization of the previously explained analysis procedure (section 4.2.4) using real microwave data. In the

1.5

1.5

real part imaginary part

1.0

22, RT cal.

)
1.0

corrected S

22

0.5

0.5

0.0

0.0

-0.5

-0.5

-1.0

-1.0

-1.5 0 10 20 30 40

-1.5 0 10 20 30 40

frequency (GHz)
14

frequency (GHz)

10000

12

Z(

8000 10 6000

4000

4 2000 2 0

-2000

-2

-4 -4000 -6 0 10 20 30 40 0 10 20 30 40

frequency (GHz)

frequency (GHz)

Figure 7.1: analysis procedure example; usually performed electronically by our Labview analysis routine (SrRuO3 on MgO spectra)

rst picture we see the spectra as returned by the network analyzer; they are corrected by the NWA with a saved calibration set belonging to a commercial room temperature calibration. In order to obtain the corrected reectivity, we have to exchange the commercial calibration by

53

7 Sr1x Cax RuO3 : Results and Discussion the temperature dependent three standard calibration. This is done in the rst analysis step between subgraphs one and two. In the second step, the frequency dependent impedance is calculated with the simple relation ZL = Z0 1 + S11 1 S11 (7.1)

The last step is to calculate the conductivity as described in section 4.2.4. It should be noted that only the calculation of the conductivity from the impedance is limited by assumptions. The preceding steps are always valid independently from lm thickness or other parameters. Although the possible frequency range reaches up to 40 GHz, the most clean and reliable data is produced at lower frequencies approximately up to 20 GHz.

7.1.1 Microwave Measurements of Samples on SrTiO3 Substrate

When the samples and their fabrication process were described in chapter 5.3, the signicance of the substrate was also discussed. From residual resistivity ratios we estimate the quality of a lm concerning the mobility of its electrons and their scattering mechanisms. From this point of view SrTiO3 would be a convenient and obvious choice: very well characterized, commercially available in high quality, it comes with a perovskite structure very similar to SrRuO3 and CaRuO3 . For optical thin lm measurements, however, it turned out to be of nearly no use. All our measurements of thin lms on this substrate (see g. 7.2) show massive background resonances. As we work in a limit where the thin lm is much smaller than the skin depth,

CaRuO

SrRuO 4

Re (Z) ()

6 4 2 0 0 10 250 20 frequency (GHz) 30 40 100 150 200 temperature (K) 300

Re (Z) ()

2 0 0 5 10 15 20 25 250 30 35 40 100 200 150 temperature 300

frequency (GHz)

Figure 7.2: real part of the impedance for CaRuO3 on SrTiO3 and SrRuO3 on SrTiO3

our electromagnetic elds penetrate the substrate as well. A large substrate are frequency independent and

of the substrate shifts its

resonances to lower frequencies, down to the microwave region. If the optical properties of the is not too large, the substrate will not disturb the measurement of the lms optical constants or their frequency dependency at low frequencies. To a very good approximation this is the case for MgO and NdGaO3 . SrTiO3 , however, is a ferroelectric material and has a very high and frequency-dependent dielectric constant. Due to this huge background a quantitative analysis of the data on these samples gives only sparse information on the thin lm itself. As a consequence, we will show the calculated conductiv-

54

7.1 Microwave Spectrometer Results ity 1 and 2 with its temperature dependence without much interpretation. In addition to the conductivity, we will also show the real part of the impedance: the resonances stemming from the SrTiO3 substrate and their temperature dependence are illustrated very well by these plots. The data is presented as three dimensional surface plots: they show frequency as well as temperature dependence. In one surface plot we include 152 spectra. They were measured at temperatures between 80 K and 300 K in 2 K intervals by an automatically operated measurement procedure. Similar to the FMR surface and gray scale plots, a regular meshgrid is calculated for the two variables frequency and temperature. For every point of that meshgrid the corresponding value is interpolated from the measured spectra. All grids and interpolations of the three dimensional plots were calculated with Matlab.

x 10 15 cm )

x 10 15 cm )
1

10 5 0 5 0 10 20 frequency (GHz) 30 40 100 150 250 200 temperature (K) 300

10 5 0 5 0 10 20 frequency (GHz) 30 40 100 150 250 200 temperature (K) 300

1 (

Figure 7.3: real and imaginary parts of the conductivity for CaRuO3 on SrTiO3

x 10 15 1 (1 cm1)

2 (

x 10

10
cm )
2

1
1

0.5 0

5 0 0 10 20 frequency (GHz) 30 40 100 150 200 250

300

0.5 1 0 10 20 30 frequency (GHz) 40 100 150 250 200

300

temperature (K)

temperature (K)

Figure 7.4: real and imaginary parts of the conductivity for SrRuO3 on SrTiO3

For both materials we can conclude the following from their conductivity spectra: imaginary parts start at 0 for low frequencies (consistent with causality), real parts at some nite conductivity value and remain almost constant with frequency (apart from the resonances), which

55

7 Sr1x Cax RuO3 : Results and Discussion is consistent with a Drude behavior for a metal. 1 values steadily increase with decreasing temperature, which proves metallic behavior: CaRuO3 on SrTiO3 : from 3400 1 cm1 at 300 K to 6860 1 cm1 at 80 K SrRuO3 on SrTiO3 : from 7080 1 cm1 at 300 K to 18790 1 cm1 at 80 K This temperature dependence of the real and imaginary parts of CaRuO3 and SrRuO3 at 45 MHz is shown in g. 7.5. Other than that, no reliable changes or trends are observable besides

2.0 1.8 1.6 1.4

2.0

Re ( ) Im ( )

1.8 1.6 1.4

Re ( ) Im ( )

cm )

1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 50 100 150 200 250 300

cm ) (10

-1

1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 50 100 150 200 250 300

-1

(10

-1

-1

temperature (K)

temperature (K)

Figure 7.5: real and imaginary parts of the conductivity for CaRuO3 and SrRuO3 on SrTiO3

the resonances. Above 10 GHz the resonances become so strong and frequent that they cover the major parts of the spectra.

7.1.2 Microwave Measurements of SrRuO3 on MgO

As SrTiO3 substrates have proven to be unsuitable for our kinds of optical spectroscopy, SrTiO3 had to be replaced by another material. The rst try was to use another very common substrate: MgO. Despite its disadvantages for this particular system (see section 5.3) it seemed to represent a valid alternative. As a matter of fact, we obtained much smoother and less overcrowded conductivity spectra (see gures 7.6). Existing resonances have almost no temperature dependence at all and are related to the substrate. Also the amplitude of the resonances is strongly reduced (compare scales: 4 DC is sucient for MgO substrate, while the SrTiO3 plots need scales of 8 DC and 15 DC ). Also the overall value range is drastically reduced: to display all points, a scale of 4 DC (where we take 1 DC for our lowest frequencies) is sucient. For SrRuO3 and CaRuO3 on SrTiO3 , plot scales of 8 DC and 15 DC are still too small to include the sharpest resonances entirely. On the other hand, characterization measurements performed by M. Schneider [3] clearly indicate a low thin lm quality. At lowest frequencies the real part of the conductivity 1 of SrRuO3 on MgO changes from 1616 1 cm1 at 300 K to 2353 1 cm1 at 80 K. The absolute value is signicantly lower than for the SrRuO3 on SrTiO3 sample from the

56

7.1 Microwave Spectrometer Results

8000 cm )
1

4000 3000

6000 4000 2000 0 0 10 20 30 40 frequency (GHz) 100 150 temperature (K) 250 200
2

1 (

2000 1000
300

0 1000 0 10 20 frequency (GHz) 30 40 100 150 250 200

300

temperature (K)

Figure 7.6: real and imaginary parts of the conductivity of SrRuO3 on MgO

last subsection. Because all lm thicknesses should be similar, the low absolute conductivity also points at the comparatively low lm quality of this sample. A clear-cut statement on the frequency-dependency is dicult to make because of the two broad resonances around 20 GHz and 35 GHz, which probably stem from the substrate. Apart from these two large features,

x 10 1 0.8 1 ( cm) 0.6 0.4 0.2 0 0

300 250 10 20 frequency (GHz) 30 150 100 40 200 temperature (K)

Figure 7.7: surface plot of the resistivity of SrRuO3 on MgO from 80 K to 300 K; the arrow indicates the kink in the resistivity at low frequencies

the real part seems to remain fairly stable with frequency. In the imaginary part there seems to be a light increase. This behavior would be consistent with a simple Drude model for a metal: at frequencies considerably lower than the scattering rate, the Drude model predicts a nearly at, slowly decaying 1 . 2 is expected as continuously increasing up to its peak at the scattering rate. For a thin lm of this quality it would not be surprising to have a scattering rate above the present frequency range and therefore any other behavior would be unconventional. Conventional metals show this Drude roll-o at frequencies in the infrared range. From this perspective, the microwave measurements of SrRuO3 on MgO do not reveal any surprising

57

7 Sr1x Cax RuO3 : Results and Discussion aspects of the sample. Fig. 7.7 shows the frequency-dependent resistivity of the sample. By looking carefully at this plot we can verify the onset of ferromagnetic order. In dc resistivity measurements like the ones shown in section 5.3, a kink in the curve indicates the onset of ferromagnetism at the Curie temperature. Due to the ordering of the magnetic moments, the scattering of the conduction electrons at these magnetic moments is reduced; this results in a reduced electrical resistivity. At 160 K the low-frequency resistivity shows a change of slope (indicated by an arrow in g. 7.7). It is not as obvious as for the samples on NdGaO3 in g. 5.3, but the samples presented there are of considerably higher quality. In the SrRuO3 on MgO thin lm we expect strongly enhanced scattering, which is also expressed in the high overall low-frequency resistivity of 0.4 - 0.6 103 cm. The magnetic scattering mechanism will contribute to the total scattering with a lower percentage than in better lms. As a consequence, the reduction of this specic mechanism will have a smaller eect on conductivity and resistivity. The kink is nevertheless present and visible also for higher frequencies, as shown in g. 7.8. In this gure, every datapoint of the shown curves is taken from another spectrum; the measurement procedure recorded a frequency-dependent spectrum every two Kelvin between 80 K and 300 K. One particular frequency is chosen, and a computer routine picks the one datapoint at this frequency from every spectrum. Five frequencies are shown: 45 MHz, 5 GHz, 10 GHz, 15 GHz and 17 GHz. The kink is visible up to high frequencies, but it is less pronounced and the slopes are less steep. Higher frequencies clearly weaken the eects of the magnetic order on the resistivity and re-introduce the scattering mechanisms of the paramagnetic phase; also the location of the kink and therefore the transition temperature is slightly lowered at higher frequencies due to the additional energy and uctuations. Other features like the occurrence of a ferromagnetic

45 MHz

5 GHz 10 GHz 15 GHz 17 GHz

(10
1

-4

cm)

50

100

150

200

250

300

temperature (K)

Figure 7.8: temperature dependence of the resistivity at dierent frequencies, the arrows indicate the location of the kink

antiresonance around the Curie temperature can not be found in this set of measurements.

58

7.2 THz Spectrometer Results

7.2 THz Spectrometer Results

0.08

300K

transmission

0.06

5K

0.04

0.02

0.00 0 1.8 10 20 30 40 50

mirror displacement

Ph 300 K Ph
1.6

5 K

1.4

1.2 0 10 20 30
-1

40

50

frequency (cm )

Figure 7.9: example of transmission and phase data for Sr0.2 Ca0.8 RuO3 for 300 K and 5 K. All samples were measured at the same frequencies at several temperatures between 300 K and 5 K.

All THz measurements that will be presented in the following section were performed on thin lm samples on NdGaO3 substrates. The main results on the Sr1x Cax RuO3 series were obtained with an aperture of 4 mm diameter using the following BWO sources: packetized OV 86 OV 86 with doubler OV 86 with tripler QS 200 yes yes yes no frequency range [cm1 ] 3.46.0 6.812.0 10.618.0 41.245.8 detector Golay cell Golay cell Golay cell bolometer

Every source was measured at the temperatures 300 K, 250 K, 200 K, 150 K, 100 K, 80 K, 60 K, 40 K, 30 K, 20 K, 15 K, 10 K, 7 K and 5 K. As the temperature dependence of the spectra below 30 K was very weak, no measurements of the doped samples below 5 K were taken. For clarity, I will usually show a representative selection of some temperatures: 300 K, 200 K, 150 K, 100 K, 60 K, 40 K, 20 K, 10 K, 5 K. A typical example is shown in g. 7.9 for two dierent temperatures and one sample. Each transmission curve consists of four dierent spectra, each phase curve of three (no phase could be measured at highest frequencies). For each sample and each temperature we obtained one transmission and one phase curve; these were analyzed and processed into eight to nine data points in frequency space (conductivity or even further processing, analysis methods see section 4.3.4). For clarity and a better overview on the broadband frequency dependency, these conductivity points will be connected by thin lines of the respective color.

59

7 Sr1x Cax RuO3 : Results and Discussion

7.2.1 Problems with the rst CaRuO3 on NdGaO3 Sample

The rst sample on a NdGaO3 substrate we obtained was CaRuO3 . It had been well characterized and shown to be of very good quality. However, during THz measurements an unexpected issue came up: the transmission through the sample depended quite strongly on the position of the beam on the sample. To ensure that the spectra of dierent sources were always taken at the same spot of the sample, many positions along the sample had to measured. For every source, the spot with the lowest transmission (and therefore highest conductivity) was chosen. Fig. 7.11 shows the seven dierent positions that were measured with a 2 mm aperture at room temperature after all measurements inside the cryostat had been completed. Beforehand, the lm thickness was determined on four dierent positions using ellipsometry: although the variable transmission had indicated an inhomogeneous lm thickness, all spots showed thicknesses between 47 and 52 nm. Nevertheless, some kind of impurity was found just by looking at how the ellipsometers beams moved along the sample surface. This was conrmed with an optical microscope. In g. 7.10, the location of the feature is indicated by a grey spot. Its position

Figure 7.10: measurement positions on the CaRuO3 on NdGaO3 sample

coincides with the enhanced transmission spectra, which are shown in g. 7.11. The change in absolute transmission ranges from around 8% to over 20%. Another surprising aspect is the fact that not only the absolute value of the transmission is changed, but also the spectra are shifted in frequency. This cannot be explained by a small variation of the lm thickness. In fact it was impossible to nd an acceptable t to the higher transmission spectra without substantially changing the substrates thickness and with it the phase. Such a large thickness variation in a commercially produced substrate would be surprising, though. Additionally, the thicknesses of all four corners of the sample were measured: they were very nearly the same and by around 20 m o the best t value for position 6. It is dicult to draw any nal conclusion from this analysis, but apparently there was an unknown feature present, corrupting the measurements in its vicinity. So far the most plausible explanation for this lies in the fabrication process: during the metalorganic aerosol deposition of this particular sample, the substrate temperature was not as high as for the subsequent samples. This might have led to a deposition of a large non-vaporized droplet onto the lm, which resulted in position-dependent optical properties

60

7.2 THz Spectrometer Results

0.25

Pos 1 Pos 2 Pos 3

0.20

Pos 4 Pos 5 Pos 6

Transmission

0.15

Pos 7

0.10

0.05

0.00 10 12 14 16
-1

18

Frequency (cm )

Figure 7.11: transmission spectra of the dierent sample spots

and unaccountable phase shifts.

Nevertheless the results of the data analysis is shown in g. 7.12 for some selected temperatures. The real part indicates the evolution of a conductivity peak at around 14 cm1 , which

3.0

0.4

300K 200K
2.5

300K 200K 100K 50K

0.3

100K 50K 20K

20K 5K

2.0
-1

5K
-1

cm

-1

cm
1.0
-1

1.5

0.2

0.1

0.5

0.0 0 5 10 15 20 25 30
-1

0.0 35 40 45 0 5 10 15 20 25 30
-1

35

40

45

frequency (cm )

frequency (cm )

Figure 7.12: real and imaginary part of the conductivity for the CaRuO3 sample

cannot be accounted for by conventional material properties. As this feature is absent in later measurements of other CaRuO3 samples, it is interpreted as an artefact of a corrupted measurement. After signicant dierences from other, better samples came up, this sample (D3) was not used for any further measurement or analysis.
1

reference: M. Schneider, personal communication

61

7 Sr1x Cax RuO3 : Results and Discussion

7.2.2 THz Results for SrRuO3 , Sr0.6 Ca0.4 RuO3 , Sr0.2 Ca0.8 RuO3 and CaRuO3
The four metallic samples SrRuO3 , Sr0.6 Ca0.4 RuO3 , Sr0.2 Ca0.8 RuO3 and CaRuO3 belong to the Sr1x Cax RuO3 doping series with a quantum phase transition at a doping of 70 %. Investigating the phase diagram of this system with optical methods was a main objective of this thesis. In this section we will show results that were obtained from transmission and phase spectra. The conductivity was obtained by tting every Fabry-P erot maximum with a Drude parameter as explained in section 4.3.4. Fig. 7.13 includes the same resistivity curves as g. 5.3. Now we

SrRuO
1.0

40% CaRuO
1.0

0.8

0.8

R/R(300K)

0.6

0.6

0.4

0.4

0.2

0.2

0.0 0 50 100 150 temperature (K) 200 250 300

0.0 0 50 100 150 200 250 300

temperature (K)

80% CaRuO
1.0

CaRuO
1.0

0.8

0.8

R/R(300K)

0.6

0.6

0.4

0.4

0.2

0.2

0.0 0 50 100 150 200 250 300

0.0 0 50 100 150 200 250 300

temperature (K)

temperature (K)

Figure 7.13: normalized resistivity data for all four samples: data obtained from THz data in the region of 5 cm1 (black single points) and dc resistivity curve measured by M. Schneider (gray)

compare the dc data that was measured with a four point dc experiment with low-frequency data from THz. The THz resistivity data is obtained by tting the Fabry-P erot maximum at lowest frequencies (around 5 cm1 ) with the usual local Drude model, which yields one DC and one damping-value. Every point represents one 1/DC value, which was normalized to the respective value at 300 K.

62

7.2 THz Spectrometer Results The overall correspondence between the two data sets is very good (except for the 250 K point in the THz data, which tends to lie below the curve). As low frequency THz data at 5 cm1 nearly coincides with dc data, we do not expect large eects at even lower frequencies. It is also a good sign concerning the quality of the measurements and the samples: despite two very dierent measurement procedures we obtain the same result. In dc measurements the current takes the one path with the lowest resistance. In THz measurements we probe a sample region of the dimension of our beam with an electromagnetic eld and extract the optical constants of this region; they represent a local average over the beam projection area. The fact that the two results are the same indicate uniform physical parameters throughout the sample and a good reproducibility of our measurement procedures. Figures 7.14 and 7.15 show the frequency-

SrRuO
11 10 9 8 7
-1

40% Ca
11 10 9 8 7 6 5 4 3 2 1
300K 250K 200K 150K 100K 60K 40K 20K 10K 5K

6 5 4 3 2 1 0 0 10 20
frequency (cm

(10

-1

cm

30
-1

40

50

10

20

30
-1

40
)

50

frequency (cm

80% Ca
11 10 9 8 7
)
cm

11 10 9 8 7 6 5 4 3 2 1 0 10 20 30
-1

CaRuO

6 5 4 3 2 1 0 40 50

(10

-1

-1

10

20

30
-1

40

50

frequency (cm

frequency (cm )

Figure 7.14: real parts of the conductivity for all samples on NdGaO3

dependent real and imaginary parts of all four samples. Absolute values of the conductivity start at approximately 0.5 104 1 for all samples at room temperature and peak at over 10 104 1 for CaRuO3 . Compared to the other studied samples on SrTiO3 and MgO, the absolute conductivity is much higher, i.e. scattering processes are considerably reduced; this exemplies to the superior quality of the new samples on NdGaO3 .

63

7 Sr1x Cax RuO3 : Results and Discussion 1 of the the SrRuO3 sample is frequency-independent in a large frequency range at low and high temperatures. At intermediate temperatures we see a slight increase at high frequencies. Absolute values show a strong increase with decreasing temperatures over the entire frequency range, which indicates that no additional strong absorption or scattering processes occur in the measured energy range. SrRuO3 shows a large increase in the imaginary part. 2 takes very high absolute values in this sample compared to the other lms: they are a factor of 6 higher than in CaRuO3 and even a factor of 60 higher than in the 40 % Ca-doped sample. While for the other lms a maximum value of 1 104 1 cm1 or 2 104 1 cm1 is sucient, 2 of SrRuO3 reaches values above 10 104 1 cm1 . The evolution of 1 and 2 at low and high temperatures is consistent with a conventional Drude behavior below the scattering rate; the increase at intermediate temperatures is very small and mainly occurs at the highest frequencies, where no phase measurement is available and the errors are larger. It is therefore hard to say if there really is a frequency dependence of the scattering rate and a disagreement with the Drude model. Summarizing the results for SrRuO3 , they are generally well explainable by a simple Drude model. The sample with 40 % Ca doping shows no frequency dependence in 1 .

SrRuO
13 12

3
2.5

40% Ca
300K 250K

11 2.0 10

200K 150K 100K

cm

-1

1.5

60K 40K 20K

-1

(10

1.0

10K 5K

3 0.5 2

0 0 10 20 30
-1

0.0 40 50 0 10 20 30
-1

40

50

frequency (cm

frequency (cm

80% Ca
2.5 2.5

CaRuO

2.0

2.0

-1

cm

-1

1.5

1.5

(10

1.0

1.0

0.5

0.5

0.0 0 10 20 30 40 50

0.0 0 10 20 30
-1

40

50

frequency (cm

-1

frequency (cm )

Figure 7.15: imaginary parts of the conductivity for all samples on NdGaO3 . Note the dierent scale for SrRuO3

64

7.2 THz Spectrometer Results There might be some upward trend (or at least some absorption feature) indicated by the very last point around 45 cm1 . Although it occurs at all temperatures, stronger evidence at higher frequencies would be needed to conrm it. In the investigated frequency range the real part of the conductivity can denitely be described as frequency independent. The absolute values are lower than for all other samples, which is consistent with the comparatively high disorder in this sample. In 2 we observe a signicant drop with doping from SrRuO3 to Sr0.6 Ca0.4 RuO3 . It is slightly increasing with frequency. Also this sample is consistent with a Drude picture below the scattering rate. In the 80 % Ca-doped sample we have a similar picture as in SrRuO3 , only at lower absolute values. While the real part is mostly frequency independent (with a slight possible upward trend at intermediate temperatures), the imaginary part increases with frequency. Also for this sample, the one closest to the quantum phase transition, there is no unconventional behavior that contradicts a Drude interpretation. Unexpectedly, the most uncommon behavior was not found in the doped samples or close to the quantum phase transition but in CaRuO3 (at least in the 5 K to 300 K temperature range). Starting from 20 K we observe a strongly enhanced conductivity at lowest frequencies with a prominent drop at intermediate ones. While the lowest frequencies t the dc resistivity well, the strong suppression of conductivity cannot be interpreted in terms of a simple Drude model. If this roll-o actually is a Drude roll-o, it should not level o so quickly but go to zero. One explanation could be a model with two dierent electronic systems and two Drude contributions, one with a high DC and very low scattering rate around 7 cm1 and another one with a lower DC and a much higher scattering rate. CaRuO3 has the highest quality and RRR value, so a Drude contribution with a small scattering rate seems reasonable; but the fact that SrRuO3 with a similar quality has a considerably higher scattering rate outside the measured frequency range does not t into this picture. While the dc conductivity of CaRuO3 is higher than in SrRuO3 by a factor of 2 at the most, the scattering rate in SrRuO3 is at least ten times higher than of the rst Drude in CaRuO3 . It also remains unclear what the physical origin of two electronic systems and two Drude contributions could be. Since all samples but CaRuO3 do not show any sign of a second Drude contribution or a roll-o, the data points to an unconventional physical meachanism particularly in this material. 2 , which is constant at high temperatures, also behaves unconventionally below 20 K. Like in 1 there is a drop in conductivity at low frequencies. Due to causality 2 has to be 0 in the 0 limit, so there has to be a maximum in 2 at lower frequencies. Another increase at intermediate frequencies and a decrease towards higher frequencies is seen for 5 K, 7 K (not shown) and 10 K. The conductivity data was further processed using the extended Drude model (see 3.1.1). In section 3.1.1 the theory was explained using CGS units. Actual calculations with experimental

65

7 Sr1x Cax RuO3 : Results and Discussion data are usually performed in SI units: ( ) = ( ) = 1 ( ) 4 0 ( ) CGS SI

By simple algebraic operations we obtain the following expressions for real and imaginary parts of the resistivity: 1 = 2 4 0 1 1 2 + 2 2 4 0 2 = 2 1 + 2 2 (7.2)

From the resistivity we can calculate the frequency-dependent scattering rate ( ) and the ratio m /m of eective mass and band mass. One unknown parameter is the plasma frequency P . Assuming a constant charge carrier density this is merely a material parameter and remains present in the equations as a constant prefactor: 1 0 1 = = 2 2 4 1 + 2 2 P 1 m 2 0 2 = = 2 2 4 (1 + 2 2 ) P m (7.3)

(7.4)

With these relations we are able to calculate and display the frequency-dependent scattering rates (7.16) and eective masses (7.17) of the four samples. Scattering rates decrease with temperature; this is well understandable and expected, as thermally activated scattering mechanisms like phonons freeze out at low temperatures. Below 20 K, the absolute value range of the scattering rates does not change any more, in correspondence with the eect observed in the transmission spectra. For SrRuO3 and the two doped samples the scattering rates slightly decrease with frequency at higher temperatures and remain constant at lower ones. However, this decrease in the SrRuO3 sample is only present due to the points at highest frequencies (where also higher errors are present); at lower frequencies the scattering rate is constant. With higher energies we would not expect a decrease in for a simple metal, as higher energies can excite the system and thus provoke enhanced scattering. If the energies are not yet high enough for signicant eects, the scattering rate should at least remain constant. However, the decrease is only small (up to 25%) and manifests itself mainly at high frequencies. A possible connection to special intraband excitations and the density of states of these materials could be investigated further by measuring also the intermediate frequencies. In the present data no strong disagreement (i.e. exceeding the error margins) with a Drude model can be conrmed for SrRuO3 and the doped samples. Especially at low energies, the agreement with a Drude

66

7.2 THz Spectrometer Results

SrRuO
3.0

40% CaRuO
3.0

300K
2.5 2.5

250K 200K

-18 s)

2.0

2.0

150K 100K

(10

1.5

1.5

60K 40K

1.0

1.0

20K 10K

0.5

0.5

5K

0.0 0 10 20 30

0.0

frequency

(cm

-1

40

50

10

20

30

frequency

(cm
3

-1

40

50

80% CaRuO
3.0

CaRuO
3.0

2.5

2.5

-18 (10 s)

2.0

2.0

1.5

1.5

P
1.0

1.0

0.5

0.5

0.0 0 10 20 30

0.0

frequency

(cm

-1

40

50

10

20

30

frequency

(cm

-1

40

50

Figure 7.16: scattering rates for all four samples

67

7 Sr1x Cax RuO3 : Results and Discussion model is quite good. For CaRuO3 , remains constant at high temperatures and slightly increases for the lowest ones. Concerning the eective masses, there are two trends: on the one hand, eective mass

100 80 60 40 20 0

SrRuO

100 80 60 40 20 0

40 % Ca
300K 250K 200K 150K 100K 60K 40K 20K 10K 5K

(1/

m*/m

(10

-30

10

20
frequency

30

-1

40

50

10

20
frequency

30 -1
(cm )

40

50

(cm )

100 80 60 40 20 0

80 % Ca

100 80 60 40 20 0

CaRuO

(1/

m*/m

(10

-30

10

20
frequency

30
-1

40

50

10

20
frequency

30

-1

40

50

(cm )

(cm )

Figure 7.17: eective mass ratios for all four samples

ratios decrease with lower temperatures. This behavior lacks a good explenation so far. An enhanced eective electron mass originates from enhanced correlations between the electrons. At higher temperatures, electronic correlations usually become weak compared to other eects. On the other hand, eective mass ratios increase with lower frequencies. Angle-resolved deHaas-van-Alph en studies showed mass enhancements by factors of 4 to 6 (depending on the respective orbit on the Fermi surface) [39] at very low temperatures around 30 mK. Such an enhancement of the eective mass is consistent with our results. Discussion with respect to Quantum Criticality Summarizing the results for the four samples on NdGaO3 substrate, we can say that the frequency-dependent conductivity is consistent with a Drude model for SrRuO3 and the two samples with 40% and 80% Ca doping. CaRuO3 shows a completely dierent behavior for tem-

68

7.2 THz Spectrometer Results peratures below 30 K. This would be consistent with the non-Fermi-liquid behavior of CaRuO3 reported in [3] in the sense that also the optical data does not follow any established model. The scattering rate is increasing with frequency in CaRuO3 for this temperature range; however it is not possible to draw conclusions on the exact functional dependence with the number of points we obtain from our optical data. For the other samples, the scattering rate is constant at low temperatures, which is again consistent with a Drude model. At high temperatures there might be a slight decrease, but it does not occur in the low-energy Fermi liquid (FL) and possible quantum-critical regions and therefore has to be caused by other eects. From our measurements we do not see any polynomial frequency dependence at low temperatures except (possibly) in CaRuO3 : neither a T 2 dependence proving a FL phase, nor a T n dependence with n = 2 proving a non-FL phase. A possible explanation lies in the connection of the FL and Drude models discussed in sections 3.1.1 and 3.4. FL theory predicts a scattering rate depending on temperature and frequency: F L = (T, ) = 1 (T ) + 2 ( ) + 0 = AT 2 + B 2 + 0 (7.5)

The constant factor 0 is caused by impurity scattering, which depends on sample quality and is an intrinsic parameter. In the case that B 2 can be neglected with respect to AT 2 and/or 0 , the FL model is reduced to the simple Drude model: Drude = (T ) = AT 2 + 0 (7.6)

As most of our measurements agree with the simple Drude model rather than with the FL one, the frequency-dependent factor seems to be negligible. If we assume a common energy scaling of kB T and , one cm1 corresponds roughly to 1 K and in most cases we will obtain kB T . For microwaves, the photon energy is very small and our accesible temperature range is not low enough to bring the thermal energy down to a comparable scale. In the microwave experiments, we do not expect to see the frequency dependency predicted by FL theory. In the THz range, the photon energies are higher and in the same order of magnitude as the thermal energies. To see the optical term of a FL phase, the frequencies have to be just high enough to outrange the thermal energy, but still low enough to ensure the applicability of the FL regime, which is only valid for low-energy excitations of the system (see also 3.4). A term that has not been discussed so far is the residual value 0 . As temperatures and frequencies become very small, 0 gets to be the leading term. To observe FL or non-FL behavior optically, this term has to be very small; i.e. the sample has to be be very pure. In thin lm samples like the ones used for these experiments, the residual scattering rate is limited, because scattering at the

69

7 Sr1x Cax RuO3 : Results and Discussion surface and at defects always occurs. As a consequence, it could be very dicult to observe FL-like frequency dependency in thin lms: very low temperatures, very high sample quality and low (but not too low) frequencies are required. From this point of view it is natural that the doped samples will not show a frequency-dependent scattering rate at low temperatures: the disorder, which is introduced by the doping and which is reected in the residual resistivity values, automatically leads to rather high 0 values. The only samples where the 2 ( ) part could be seen in our experiments are SrRuO3 and CaRuO3 . In CaRuO3 we see an increase in at low frequencies, in SrRuO3 the scattering rate is constant. Nevertheless a conclusion with respect to quantum criticality of these materials cannot be drawn from the scattering rate data; but it becomes clear that with more points and an even lower residual scattering rate we could denitely investigate this issue with THz spectroscopy in a CaRuO3 sample. Thinking of the theoretical phase diagram of a quantum critical system (g. 3.4) and the phase diagram of Sr1x Cax RuO3 with the non-FL regions reported in literature (g. 2.1), we can conclude the following: our optical data for SrRuO3 and the doped samples was consistent with a Drude model also in the reported non-FL regions for SrRuO3 [5] [6] (from infrared conductivity), and rather agree with the conventional metallic behavior reported in [3]. Also in the non-FL region in CaRuO3 at high temperatures, reported in [7], our optical data shows a simple Drude behavior. Clear deviations from Drude and FL models were found in our optical data for CaRuO3 in the same temperature region where non-FL behavior was reported in [3] (from dc measurements). In the same measurement series of [3], also 80% Ca-doped samples showed non-FL behavior. From our optical data, the 80% doped sample agrees well with a Drude model. An important dierence compared to our SrRuO3 and CaRuO3 data is the RRR value: it is much higher in the doped samples, the absolute values of the optical conductivity are much lower and the 0 term also is much higher. It is possible that for these samples the residual scattering rate is the main contribution to the optical data and covers other eects like the roll-o in CaRuO3 .

70

8 Summary and Outlook

We performed measurements with low-energy optics at cryogenic temperatures on several metallic thin lm samples of 40 nm to 90 nm thickness. As spectroscopic methods we used broadband microwave spectroscopy on the one hand and frequency domain THz spectroscopy on the other. We addressed the frequency-dependent behavior of the system Sr1x Cax RuO3 with a ferromagnetic quantum phase transition at x 0.7. Furthermore, we investigated ferromagnetic resonance in SrRuO3 and two other interesting ferromagnetic materials: Permalloy (Ni80 Fe20 ) and a Heusler alloy (Co2 Cr0.6 Fe0.4 Al). For the microwave measurements we applied two dierent techniques: investigations of the frequency-dependent conductivity were performed on the three samples CaRuO3 on SrTiO3 , SrRuO3 on SrTiO3 and SrRuO3 on MgO, using a Corbino reection setup. Investigations of the ferromagnetic resonances were performed on four samples using broadband transmission spectroscopy: one Permalloy thin lm and one Heusler thin lm, SrRuO3 on MgO and SrRuO3 on SrTiO3 . While the Corbino method requires a careful calibration in order to obtain precise values for the frequency dependent impedance and conductivity, the transmission method is only used to obtain relative intensities with a simple normalization. All microwave measurements were recorded with a HP 8510 network analyzer; for both methods the microwave signal was transmitted to the sample holder through semi-rigid coaxial cables and passed onto the pins (center pin for Corbino, two side pins for transmission) by microwave connectors. The electric and magnetic elds of the microwave signal penetrate the thin lms and probe their electromagnetic properties. With the transmission method, we were able to establish a working broadband measurement procedure for ferromagnetic resonances: using permanent magnets, we were able to apply a variable magnetic eld with a maximum ux density of 168 mT at the location of the sample. The ux density was changed mechanically by varying the distance between the two magnets. We showed that there is no eect of the magnetic eld in the region from 45 MHz to 10 GHz in the empty setup and in a non-magnetic NiCr thin lm sample. The ferromagnetic reference sample Permalloy presented a small but clear resonance, whose frequency shifted from around 3.5 GHz to 9 GHz for magnetic elds from 18 mT to 148 mT. Also the Heusler thin lm presented a resonance, shifting from 5.5 GHz to 9 GHz for the same magnetic eld range. From the resonance widths we calculated a damping factor of = 0.097 0.37 for this material. No FMR was observed for the ferromagnetic thin lm SrRuO3 in the microwave region: despite repeated measurements on two dierent samples (one on SrTiO3 and one on MgO substrate),

71

8 Summary and Outlook no frequency- and eld-dependent resonance peak could be resolved with our present experimental resolution. This is consistent with the exotic FMR reported in SrRuO3 at much higher frequencies of 250 GHz [1]. Detection of an FMR was also attempted in reection geometry, but neither Permalloy nor the Heusler sample showed any sign of it. One possible reason is that the eld-dependent substrate and setup resonances are more pronounced there. Nevertheless, a complete absence of any FMR trace in all our thin lm samples is not understood, especially because a strong FMR signal was detected with Corbino geometry in single crystal samples in [2]. Most Corbino measurements were devoted to nding the frequency-dependent conductivity in SrRuO3 and CaRuO3 . The samples on the ferroelectric SrTiO3 substrate were dicult to analyze because of the strong and frequency-dependent substrate resonances. SrRuO3 on MgO was free of such resonances, but the lm quality was considerably lower than for the other substrates due to a high lattice mismatch. In summary, no inconsistencies with a Drude model for metals were found in the microwave measurements. Four samples of the Sr1x Cax RuO3 series on a NdGaO3 substrate were measured with the quasi-optical THz spectrometer. Their transmission and phase was measured in a frequency range of 5 cm1 to 18 cm1 and 41 cm1 to 46 cm1 (150 GHz to 540 GHz and 1.23 THz to 1.38 THz) and at dierent temperatures ranging from 2 K to 300 K. For all samples, the spectra below 20 K were very similar to one another;therefore only spectra above 5 K were analyzed. From the Fabry-P erot oscillations of transmission and phase of the thin lm samples and their substrates, conductivity values were calculated for every oscillation with a two-layer model (dielectric substrate with metallic lm). The obtained resistivity at lowest frequencies coincides very well with four-probe dc measurements of these samples, which proves on the one hand the accuracy of our data and on the other hand indicates that nothing spectacular happens at lower frequencies. SrRuO3 and the 40% and 80% Ca-doped samples showed a constant real part and an increasing imaginary part, which is consistent with a Drude model. In CaRuO3 real and imaginary parts of the conductivity are suppressed for frequencies higher than 10 cm1 for temperatures below 30 K. This cannot be explained by a simple Drude model or FL theory and indicates the presence of other mechanisms. Around the same temperature range, non-FL behavior was found in CaRuO3 from dc resistivity [3]. In an extended Drude analysis, the scattering rates and eective mass ratios were calculated. SrRuO3 and the doped samples had constant to slightly decreasing scattering rates, while CaRuO3 had constant scattering rates at higher temperatures and slightly increasing scattering rates below 30 K. A power-law exponent of the increase could not be calculated with this dataset, but its presence shows that in this sample potential FL or non-FL behavior could be resolved. SrRuO3 and the doped samples generally show conventional metallic Drude behavior, while CaRuO3 measurements show signicant discrepancies with Drude and FL models and are consistent with a non-FL phase at low temperatures.

72

With the experiments and results presented in this work, many interesting and challenging future tasks come up: concerning the FMR measurements, the entire setup can be optimized further. Some stainless steel setup parts were slightly magnetic and could be replaced by nonmagnetic parts to make sure they do not interfere with the measurement. Setup and substrate contributions as well as standing waves should be reduced as much as possible by optimizing measurement procedures, reproducibility, sample substrates and geometries. Further measurements in Corbino geometry with thin lms as well as single crystals could reveal the reasons for the diculties of the reection FMR measurements. For the Sr1x Cax RuO3 system there are many possible future steps: the samples on NdGaO3 are very well suited for our experiments and have a very high quality. In order to obtain more information on the phase diagram, more samples with dierent Ca content should be measured in the THz range with the same routine. Furthermore, an extension of the frequency range for all samples would be desirable. Particularly the frequencies between 18 cm1 and 41 cm1 should be addressed. Small trends, which can only be suspected in the present measurements, could be conrmed or excluded if the entire frequency range from 5 cm1 to 46 cm1 was available. Additionally the evolution of the conductivity at higher frequencies could also be addressed using infrared spectroscopy. Especially for the detection of the frequency-dependent part of the FL theory, measurements at temperatures below 2 K are desirable. For the same purpose, thin lms with an even lower residual scattering rate might be needed. One downside of a higher conductivity is a reduced transmission, but to a certain extent this can be compensated e.g. by using the bolometer for all frequencies. Especially in the case of CaRuO3 an alternate data analysis would be helpful in order to determine the power-law dependence at low temperatures: from transmission and phase measurements, a point-to-point analysis could be performed and would yield a continuous curve. For such an analysis, a more elaborate phase correction with respect to a phase oset would be necessary. All these suggested measurements could reveal further information on the phase diagram for Sr1x Cax RuO3 and improve our physical understanding of this ferromagnetic quantum phase transition.

73

Acknowledgements
I would like to thank the following people: Prof. Dr. Martin Dressel for giving me the opportunity to conduct the research for this diploma work at his institute Prof. Dr. J org Wrachtrup for co-reviewing my thesis my supervisor Dr. Marc Scheer, who constantly supported my work through discussions, suggestions and good advice, and who spent many hours in the lab with me Melanie Schneider, who fabricated the Sr1x Cax RuO3 samples and provided helpful information, data and ideas about them and their measurements Katrin Steinberg for showing me the ropes in the microwave lab and helping me with Origin- and Labview-problems all people in the microwave lab and especially Christian Fella for helpful discussions about physics, computer issues and many other things Paul C. Martin for assisting me with many FMR measurements at the small cryostat Boris Gorshunov for helping me with the THz spectrometer Sabrina Haas for showing me how to work with a bolometer Thomas Weig for keeping me company during many THz measurements Julia Braun for kindly measuring and analyzing my rst CaRuO3 on NdGaO3 sample with the ellipsometer Gabi Untereiner for technical support for all samples and with the optical microscope Christian Cervetti for performing STM measurements Markus Stipp for computer troubleshooting Nicholas Shore for proofreading, discussions, and supporting and motivating me my parents and grandparents, whose support was essential in many ways during my studies

75

Declaration
Ehrenw ortliche Erl arung
Ich versichere hiermit, dass ich diese Diplomarbeit selbstst andig verfasst und keine anderen als die angegebenen Quellen und Hilfsmittel benutzt habe.

Declaration of Authenticity
I declare that the work in this assignment is completely my own work. No part of this assignment is taken from other peoples work without giving them credit. All references have been clearly cited.

Diana Geiger

77

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