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Raman Spectroscopy of Metal/Organic/Inorganic

Heterostructures and Pentacene-Based OFETs

von der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz genehmigte Dissertation zur Erlangung des akademischen Grades

doctor rerum naturalium (Dr. rer. nat.)

vorgelegt von MSc. Phys. Beynor Antonio Paez-Sierra geboren am 24. September 1971 in Florián-Santander

eingereicht am 06. März 2007

Gutachter:

Prof. Dr. Dr. h.c. Dietrich R. T. Zahn Prof. Dr. Veit Wagner Prof. Dr. Michael Hietschold

Tag der Verteidigung: 20. Dezember 2007

http://archiv.tu-chemnitz.de/pub/2008

B. A. Paez-Sierra, Dedication

ii

Dedication

This thesis is dedicated to my wife Viktoriia

B. A. Paez-Sierra, Bibliografische Beschreibung

iii

Bibliografische Beschreibung

MSc. Phys. Beynor Antonio Paez Sierra Raman Spectroscopy of Metal/Organic/Inorganic Heterostructures and Pentacene-Based OFETs Technische Universität Chemnitz Dissertation (in englische Sprache), 2007

Im Rahmen dieser Arbeit wurden die Wechselwirkung von Indium (In) und Magnesium (Mg) als Topelektroden auf zwei Perylen-Derivativen, 3,4,9,10-Perylentetracarbonsäure Dianhydrid (PTCDA) und Dimethyl-3,4,9,10- Perylentetracarbonsäure Diimid (DiMe-PTCDI) untersucht. Die Metal/organische Schichten wurden auf S-passivierten GaAs(100):2x1-Substraten hergestellt und unter Ultrahochvakuum (UHV)-Bedingungens aufgedampft. Als Hauptcharakterisierungsmethode wird die Raman-Spektroskopie eingesetzt, die eine nicht-destruktive Methode ist, und auch in situ Untersuchungen des Wachstumsprozesses ermöglicht. Die experimentell Ergebnisse haben gezeigt, dass alle aufgedampft Metallen auf die organische Schichten von PTCDA und DiMe-PTCDI eine Verstärkung des aktive Raman Signals von interne Schwingungsmoden fördern, begleitet durch die Aktivierung von normalerweise Infrarotaktivemoden. Diesem Phänomen als Oberflächenverstärkte Raman-Spektroskopie (SERS) genannt ist. Die Verstärkungsfaktoren sind in bereich von 10 1 zu 10 2 für die chemische Verstärkung und von 10 1 zu 10 4 für die Elektromagnetische Verstärkung. Interessant war, dass das In Wachstum auf PTCDA und DiMe-PTCDI nur eine Einfluss auf der Molekülgeometrie hat, und mit eine starker Diffusion durch die PTCDA- als in DiMePTCDI- Schichten. Das Mg Wachstum auf beiden Molekularstrukturen wurde durch die viel niedrigere Diffusion des Metalls in die organischen Molekülen im Vergleich zum Indium, es war durch die Bewahrung des von externe molekulare Schwingungsmoden nach das Metallswachstum, und in ersten Mal in einem Ramanexperiment beobachtet. Die PTCDA/Mg Strukturen formen sich durch zwei Stufen des Metallwachstum, die erste gehört zu einer neuen molekularen Struktur für eine Mg Schicht dünner als 2.8 nm, wo das PTCDA Molekühl des Sauerstoff-Atoms von die dianhydride Gruppe verliert. Die zweite gehört zu das SERS Spektrum von die vorherige Struktur. Im Fall von Mg/DiMe-PTCDI Heterostrukturen, den Molekühl wird gut bewahrt, wo die Raman Verschiebung an der diimide Gruppe wird nicht modifiziert. Auch von dieser Struktur eine interessante Eigenschaft wurde durch die Kopplung zwischen diskret Moleküleigenschwingungen am 221 cm -1 , 1291 cm -1 und 1606 cm -1 des organischen Materials und den elektronischen Kontinuum-Zuständen des Mg-Metallkontakts. Ihre entsprechenden Energieliniengestalten werden gut durch die Breit-Wigner-Fano-Funktion beschrieben. Die Untersuchungen auf dem vorherigen Heterostrukturen half, die Kanalbildung von Pentacen-basierten organische Feldeffekt-Transistoren (OFETs) experimentell zu analysieren, und in ersten Mal in einem Ramanexperiment durchgeführt. Der organische Kanal war gebildet durch die organische Molekularstrahldeposition (OMBD) unter UHV-Bedingungens der Pentacen Moleküle, und es war mit eine Evaporationsrate von ca. 0.65 Å/min aufgedampft. Nach jede Aufdampfung von ca. 0.1 nm des organische Moleküle, den Strom und den Ramansignal in den Kanal wurden in situ gemessen. Die minimale nominelle Dicke des organischen Materials erforderlich für den effizienten Ladungstransport durch den OFET Kanal wurde um ungefähr 1.5 nm nomineller Einschluss oder 1.1 Monolagen (ML) zu sein. Eigenschaften der ersten Monolagen werden gut im Vergleich mit dickeren Schichten definiert, wo die 1.1 ML eine gestrecktes Natur wegen seines direkten Kontakts mit dem Gate-Isolator präsentieren. Es wurde gefunden, dass der leitende organische Kanal bzw. -organische erhöhende Schicht (OBL)- eine Druckdeformierung hat. Dieses Phänomen durch die rote Verschiebung der Ramanbanden beobachtet war. Das Ausgangskennlinienfeld des OFETs wurden nach die letzte aufgedampft organische Schicht gemessen. Es wurde gefunden, dass der Drain-Strom einem Relaxationsprozesse mit zwei Zeitkonstanten hat, wo eine in der Ordnung von 10 1 min ist und die zweite unter 10 2 min. Ein ähnliches Experiment mit der Beleuchtung des Kanals mit einer 676.4 nm Laserquelle, es erhöht der Drain- Strom und lässt ummodifiziert die Zeitkonstanten. In der Ergänzung, die OFET-Strukturen waren ex situ durch Landungstransientspektroskopie (QTS) unstersucht. Die QTS Spektren zeigten positive und negative Banden zum Gesamtsignal der relaxierte Ladung in Bezug auf die einzigartige Biaspulsepolarität. Wir haben dieses Phänomen als ,,anomales Verhalten des QTS-Signals“ genannt, und in ersten Mal in einem QTS-Experiment beobachtet. Bei Wiederholung der QTS-Messung innerhalb ca. 100 min, die QTS-Spektre eine langsame Relaxationsprozesse von Störstellen am 5 μs in bereich ca. 63 min < 10 2 min hat. Die Einfangsquerschnitten sind Zeitabhängig, es bedeutet, dass die Störstellendichte nicht Konstant im Lauf der Betriebs des OFET bleibt. Dafür des Drain-Strom verändert sich und die Beweglichkeit unabhängige des elektrisches Feld ist. Experimentell Untersuchungen auf dem OFETs mit der Kombination der Ramanspektroskopie und elektrischen Felder zeigten eine Erhöhung des Ramanseinfangsquerschnitt in endliche Bereich als die chemische SERS-Verstärkung von In bzw. Mg auf die Perylen-Derivativen PTCDA und DiMe-PTCDI. Nach den Ausschaltung des elektrisches Felds den Ramansignal des Pentacen-basierten OFET eine Relaxationsprozesse mit Zeitkonstant von ca. 94 min hat. Deshalb ist die Summe von Störstellensdichte wegen dieser am organische/anorganische Grenze plus dieser dass die elektrisches Felds am die organische Halbleiter induziert.

Schlagwörter Organische Moleküle, Organische Molekularstrahldeposition (OMBD), In, Mg, GaAs(100), Grenzflächen, Ramanspektroskopie, Oberflächenverstärkte Raman-Spektroskopie (SERS), Fanoresonanz, organische Feld-Effekt Transistor (OFET), Landungstransientspektroskopie (QTS), Störstellen, organische erhöhende Schicht (OBL), Beweglichkeit, Modellbildung, Aktivierungsenergie, Ladungsdichte, Stromsrelaxation.

B. A. Paez-Sierra, Table of contents

iv

Table of contents

Bibliografische Beschreibung……………………………………………………………….…

ii

Dedication………………………………………………………………………………

iii

……… Table of contents………………………………………………………………………………

….

…….

iv

List of abbreviations…………………………………………………………………………

viii

Chapter 1. Introduction……………………………………………………………………

…….

1.1

1.1. A brief historic review of organic materials …………………………………………

1.1

1.2. Investigation of organic/ anorganic heterostructures …………………………………

1.2

References……………………………………………………………………………

………

1.4

Chapter 2. Fundamentals of molecular structures and Raman spectroscopy …………………. 2.1 2.1 Aromatic molecules……………………………………………………………………….… 2.1

2.2. The Benzene ring and π-electron delocalization…………………………………… ……

2.2

2.3. Organic semiconductor solid…………………………………………………………

2.2

2.4. Transport in organic materials………………………………………………………

….…

2.3

2.4.1. Some input parameters for the coupled electron-phonon system………………

2.4

2.4.2. Field effect mobility………………………………………………………

………

2.5

2.5. Light-matter interaction……………………………………………………………

……

2.7

2.5.1. Raman spectroscopy………………………………………………………………….

2.9

2.5.2. Basic theoretical background on Raman spectroscopy…………………………

….

2.9

2.5.2.1. Classical description of the Raman effect……………………………

……

2.9

2.5.2.2. Quantum mechanical description of the Raman effect…………………

2.10

2.5.3. Surface-enhanced Raman scattering (SERS)…………………………………

….….

2.14

2.5.4. Combined Raman spectroscopy with electric fields…………………………

……

2.16

References………………………………………………………………………………

……

2.17

Chapter 3. Experimental techniques, materials, and algorithms…………………………

3.1

3.1. Combined Raman Spectroscopy and electrical characterization setups……………

……

3.1

3.2. Sulphur passivation of GaAs(100)………………………………………………

………

3.3

3.3. Materials and structures……………………………………………………………………. 3.3.1. Structures I. Perylene derivatives thin films capped by metallic overlayers of

3.3

Indium and Magnesium……………………………………

3.4

…………………………… Molecular beam deposition (MBD) and metal evaporation…………

3.3.1.1.

…… 3.3.2 Structures II. Pentacene and C 60 organic molecules as active layers in field effect

3.4

B. A. Paez-Sierra, Table of contents

v

devices………………………………………………………………………………

……

3.6

3.3.2.1. Molecular structures: Pentacene and C 60 …………………………………

3.6

3.3.2.2. Field effect structures……………………………………………

…………

3.8

3.3.2.3. Molecular beam deposition: pentacene and C 60

………… ……………

3.8

3.4. Charge transient spectroscopy (QTS)…………………………………………

………

3.9

3.4.1. Shallow and deep level states in semiconductors……………………………

……

3.9

3.4.2. The charge transient spectroscopy (QTS) technique………………………

………

3.12

3.5. Algorithms for data evaluation and simulations………………………………………

3.14

3.5.1. Gauss-Legendre quadrature……………………………………………………

3.14

3.5.2. QTS spectra line-profile……………………………….………………………

3.15

3.5.3. Correlated fitting algorithm…………………………………………………….…

3.15

References…………………………………………………………………………

…………

3.16

Chapter 4. Metal / Organic interface formation investigated by in situ surface-enhanced Raman spectroscopy (SERS)……………………………………………………………………

4.1

4.1. Introduction………………………………………………………………………………… 4.2

4.2. Interaction of metals with perylene derivatives…………………………………………

4.3

4.3. Morphology of the metal film……………………………………………………………

4.6

4.4. Phonons and interface structural properties…………………………………………….….

4.10

4.5. Mg/DiMe-PTCDI structures and discrete-molecular coupling with continuum electronic

metal states……………………………………………………………………………………

4.13

4.6.1. Chemistry, metal film morphology and metal indiffusion……………….…………

4.13

4.6.2. Coupling of vibrational modes and electronic excitations…………………….……

4.15

Conclusions……………………………………………………………………………….….… 4.18

References……………………………………………………………………………………

 

4.18

Chapter 5. Organic Field Effect Transistors (OFETs)………………………………………

….

5.1

5.1.

Introduction…………………………………………………………………………………

5.1

5.2. Statistical mechanics of charge carriers…………………………………………………

 

5.3

 

5.2.1.

Density of states………………………………………………………………………

5.3

5.3.2 Charge carriers density…………………………………………………………….….

5.3

5.3.3.

Fermi integral argument……………………………………………………………

5.4

5.4. Charge carrier density of organic materials………………………………………………

 

5.5

5.5. The field effect transistor (FET)

….….

5.8

 

5.5.1.

Energy band structure of an OFET

….

5.9

5.6. Output characteristics of the OFET………………………………………………………

5.10

 

5.6.1.

,,Linear” regime………………………………………………………………………

5.10

B. A. Paez-Sierra, Table of contents

vi

5.6.3. Field effect mobility

μ

eff

….

5.7. Threshold voltage shift and field dependence……

Conclusions………………………

References………………………….………………………………………………………

……………………………………….

………………………………………………………….…

5.13

5.16

5.18

5.18

Chapter 6. Combined Raman spectroscopy and electrical characterization of the conductive channel in OFETs…….………………………………………………….…………………………

6.1

6.1. Introduction………………………………………………………………………………… 6.2

6.2. Simultaneous in situ I - V characterization and molecular vibration measurements of OFETs………………………………

6.3. Organic boosting layer (OBL) in OFETs….……………………………………………

6.4. Characteristic regions of the organic layer in OFETs…….…………………………

6.10

6.12

6.15

References………………………………………………………………………………………. 6.19

6.18

6.7. Bias-stress effects and multi-exponential current relaxation……………………………….

Conclusions…………………………………………………………………………………

6.5. Organic – Insulator electrodynamics…………………….……………………………

6.6. Vibrational bands profiling of the active layer………….……………………………

6.3

6.7

6.9

…………………………………………………….……

……

Chapter 7. Influence of electric fields and illumination in OFETs…………………………

….

7.1

7.1.

Introduction…………………………………………………………………………….…

7.1

7.2. Raman bands and external electric fields……………… …………………………

7.2

 

7.2.1. Band gap modification by external electric fields………………………….………

7.3

7.2.2. Raman bands alteration by external electric fields……………………………

…….

7.5

7.2.2.1. Pentacene…………………………………………………………………

7.5

7.2.3. The C 60 fullerene………………………………………………………………

….…

7.9

7.3.

Illumination and charge transport in OFETs……………………………………………

7.11

7.3.1.

Persistent effects and multi-exponential kinetics…………………………………….

7.11

Conclusions…………………………………………………………………………………

7.13

References…………………………………………………………………………………….…

7.14

Chapter 8. Trap distribution in OFETs and anomalous QTS…………………………….……

8.1

8.1. Introduction……………………………………………………………………….………

8.1

8.2. Traps and charge density distribution…………………………………………….………

8.3

 

8.2.1.

Effect of the electric field………………………………………………….…………

8.3

8.3. Anomalous behavior of the QTS signal…………………………………….………………

8.7

 

8.3.1. Advantage of floating gate configuration in QTS measurements……….……………

8.7

8.3.2. OFET devices with interdigitated source-drain electrodes…………….……………

8.8

8.3.3. Single channel OFET devices……………………………………………

………….

8.10

B. A. Paez-Sierra, Table of contents

vii

8.5. Current collapse…………………………………………………………………………….

8.17

8.5.1. Negative conductance and photodetachment………………………….……………

8.17

8.5.1.1. Charge conservation and photodetachment…………………….…………….

8.19

8.6. Photodetachment………………………………………………………

…………………

8.19

Conclusions………………………………………………………………

…………………….

8.20

References……………………………………………………………………………………….

8.21

Chapter 9. Summary……………………………………………………………………………….

9.1

List of figures………………………………………………………………………………………

10.1

List of tables………………………………………………………………………………………

10.7

Erklärung

10.8

Curriculum Vitae

10.9

List of publications…………………………………………………………………………………

10.13

Acknowledgements…………………………………………………………………………………

10.16

B. A. Paez-Sierra, List of abbreviations

viii

List of abbreviations

AFM

Atomic Force Microscopy

B3LYP

Becke’s three parameter hybrid functional

BWF

Breit-Wigner-Fano

cf.

Confer

CCD

Charge-Coupled Device

CT

Charge Transfer

DFG

Deutschen Forschungsgemeinschaft

DFT

Density Functional Theory

DH4T

Dihexylquaterthiophene

DLTS

Deep Level Transient Spectroscopy

DiMe-PTCDI

N-N’-dimethyl-3,4,9,10- perylene tetracarboxylic diimide

DIODE

Designing Inorganic/Organic Devices

EFMPM

Electrostatic Force Microscopy Phase Mode

FET(s)

Field Effect Transistor(s)

gIRSE

generalized Infrared Spectroscopy Ellipsometry

HOMO

Highest Occupied Molecular Orbital

IPES

Inverse Photoemission Spectroscopy

IRAV

Infrared Active Vibrational

IR

Infrared

I-V

Current-Voltage

LED(s)

Light Emitting Diode(s)

LO

Longitudinal Optical

LUMO

Lowest Unoccupied Molecular Orbital

MBD

Molecular Beam Deposition

ML

Mono Layer

MML

Multi Mono Layers

MOSFET

Metal-Oxide-Semiconductor Field Effect Transistor

NEXAFS

Near Edge X-Ray Absorption Fine Structure

OBL

Organic Boosting Layer

OFET(s)

Organic Field Effect Transistor(s)

OLED(s)

Organic Light Emitting Diode(s)

B. A. Paez-Sierra, List of abbreviations

ix

P3HT

Poly(3-hexylthiophene)

PABA

Para-Amino-Benzoic-Acid

PCBM

[6,6]-Penyl-C61-butyric acid methyl ester

PEI

Polyethylenimine

PTCDA

3,4,9,10-perylene tetracarboxylic dianhydride

QTS

Charge Transient Spectroscopy

RS

Raman Spectroscopy

RSS

Raman Scanning Spectroscopy

(S)FWHM

(Semi) Full Width at Half Maximum

SERS

Surface-Enhanced Raman Scattering

SFG

Sum Frequency Generation

SML

Submonolayers

MESFET(s)

Metal Semiconductor Field Effect Transistor(s)

MIS

Metal Insulator Semiconductor

PPM

Pentagonal Pinch Mode

RFID

Radio Frequency Identification

SKPM

Scanning Kelvin Probe Microscopy

SWCNT(s)

Single-Wall Carbon Nanotube(s)

TFT(s)

Thin Film Transistor(s)

TPD

Thermal-Programmed Desorption

UPS

Ultraviolet Photoemission Spectroscopy

UHV

Ultra High Vacuum

UV-vis

Ultraviolet-visible Spectrophotometry

VHR

Variable Hopping Range

XRD

X-Ray Diffraction

α -T6

α -sexithiophene

Chapter 1. B. A. Paez-Sierra, Introduction

1.1

Chapter 1 Introduction

1.1. A brief historic review of organic materials

Carbon-based compounds are considered the fundamental core of organic materials. These molecules provide a rich variety of properties, attractive for fundamental investigations in physics, chemistry, biology, engineering, and material sciences [Reic2005]. Therefore, special interest has been focused on the structural, reactive, and transport properties of such materials.

Through careful design and manipulation of a wide range of carbon-based structures, organic materials have been implemented as hybrid structures, capable of acting as electronic conductors, semiconductors, and insulators. In the electronic field, pioneering research based on organic materials dates back to the early 1900s, when the aim was to identify changes in the electrical conductivity of an alcoholic solution of eosin due to its fluorescence [Nich1904, Regn1903], and, in a similar manner, with anthracene [Howe1910]. Later on, in the late 1940s, organic molecular films were produced under vacuum conditions and revealed semiconducting properties [Pope1999].

Parallel to the experimental activity, numerous theoretical studies related to the ground state energy in benzene, azulene, naphthalene, anthracene, tetracene (naphthacene), and pentacene were carried out [Mann1949, Pari1956]. Also, electrical conductivity measurements on metal-free (mf) phthalocyanine (Pc) [Fiel1957, Heil1962], and on several metal Pcs (mPcs) with central metal atom like Cu, Ni, Co, Mn, and Fe, were performed, where a thermoelectric power of about + 50 μV / °C for mf-Pc and

CuPc was measured, proving in this way the dominant p-type character of the molecules [Fiel1957]. An interesting complement related to electronic properties of organic solids and based on mf-Pc was summarized in a publication issued in 1960 [Toll1960]. On the other hand, the n-type organic counterpart dates back to a work reported in 1961 by Kommandeur and Hall [Komm1961]. The research was performed on pyrene-iodine and perylene-iodine samples, where a high electronic conductivity in these organic molecules was recorded. Another important issue is that of charge trapping phenomena, with a pioneering investigation into Pc single crystals reported by Barbe et al.

[Barb1970].

Chapter 1. B. A. Paez-Sierra, Introduction

1.2

Particularly in the last 40 years, markedly growing research activity in the field of organic materials has been registered, with greater emphasis on two well-linked aspects, namely fundamental research and technology, during the past decade. Currently, research on large or small organic molecules for organic-based electronics is huge [Klau2006]. Applications range from single organic-based devices, i.e., diodes, transistors, light emitting devices (LEDs) [Kali2005], and gas sensors, towards more sophisticated structures, such RF identity tags, large area solar cells, passive and active-matrix light- emitting displays [Hadz2000, Kafa2005, Klau2006, Some2005].

Consequently, many investigations are targeted at understanding the electronic and chemical structure of organic/inorganic interfaces and bulk-organic materials in order to tune the device performance [Kahn2003, Scot2003, Zahn2005-2006]. In general, the physical and chemical properties of small conjugated molecules and semiconducting or metallic polymers [Brüt2004, Heeg2001] make them challenging candidates to solve drawbacks of the silicon-based devices, i.e., temperature processing, the ability to be structured on plastic substrates and low-cost production.

The investigated aromatic molecules, namely the perylene derivative 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), N,N’-dimethylperylene 3,4,9,10-dicarboximide (DiMe-PTCDI), C 60 , and pentacene, have served as prototype molecules to assemble different organic-based structures. Experiments have probed n-channel transistors based on PTCDA [Ostr1997, Xue2004], n-alkyl perylene diimides [Ches2004], and C 60 [Koba2003]; while p-channel OFETs have been realized with pentacene and many other organic molecules [Klau2006]. Still, the efficiency of p-channel OFETs is well above the most efficient n-channel organic-based transistor. Other devices, named diodes, have been demonstrated with In/PTCDA/Ag [Hude2002-2003] and Ag/DiMe-PTCDI/GaAs heterostructures [Thur2005].

1.2. Investigation of organic/ anorganic heterostructures

Several devices based on organic molecules have demonstrated the reliability of a new electronic era. Particularly, the organic field effect transistor (OFET) has been shown to be one of the most promising structures to be coupled as a key building block in complex technological applications [Bao2006, Hadz2000, Klau2006, Some2005]. Although the field effect transistor (FET) device has been known since the previous century and was proposed by Lilienfeld between 1926 and 1933 [Klei1998], there are still several challenges to be examined in order to understand the OFET version.

Several factors can influence the OFETs' performance, i.e., substrate handling, electrodes patterning, organic material purification, environment, and formation of interfaces, among others. Within the framework of the present research, special interest was addressed to the strategic features presented in Figure 1.1; they consist of an inorganic semiconductor/organic semiconductor/metal heterostructure.

Chapter 1. B. A. Paez-Sierra, Introduction

1.3

The project in which the present research activity was included was called, "Organische Feldeffekt- Transistoren: strukturelle und dynamische Eigenschaften“, or in its English version, “Organic Field Effect Transistors: Structural and Dynamical Properties”. This was a six-year project, started in 2001 and supported by a grant from the ",Deutsche Forschungsgemeinschaft,DFG” (German Research Society). The project was coordinated by Prof. Dr. Christoff Wöll of Ruhr Universität Bochum. More than 20 academic institutions, mainly from Germany, participated in this research [ofet].

mainly from German y, participated in this research [ofet]. Figure 1.1. Organic materials forming different in

Figure 1.1. Organic materials forming different interfaces, i.e.metal / organic semiconductor/ inorganic semiconductor heterostructure.

The contribution of the present work is the investigation, using combined Raman spectroscopy (RS) and electrical characterization of OFETs, as well as in situ RS of organic/metal interface formation of perylene derivatives PTCDA and DiMe-PTCDI with top metal contacts indium and magnesium (cf. Figure 1.1). Concerning the latter, previous studies were devoted to the same perylene derivatives, with Ag as top electrode [Paez2003, Salv2003, Zahn2004].

This thesis is organized as follows: Chapter 2 outlines an introduction to the fundamental aspects of aromatic molecules and their role in building up the molecular solid. Additionally, the basic theoretical background of Raman spectroscopy (RS), surface-enhanced RS (SERS) and the combined external- applied electric fields with RS, important to characterize the heterostructures and OFET devices, is presented.

In chapter 3, the experimental setups, i.e., RS, charge transient spectroscopy (QTS) and current- voltage, are discussed. Afterwards, the procedures related to substrate preparation, molecular beam deposition and metal evaporation (In, Mg), and the algorithms developed to analyze the measured data are described. In chapter 4, the in situ measurements of RS and SERS of the interface formation

Chapter 1. B. A. Paez-Sierra, Introduction

1.4

between the metals indium and magnesium onto the perylene derivatives PTCDA and DiMe-PTCDI deposited on S-GaAs substrates are analyzed.

The field effect transistor theory and its drawbacks, together with further improvements probed by experimental measurements, are addressed in chapter 5. In chapter 6, the in situ combined Raman spectroscopy and electrical characterization of the conductive channel in OFETs are presented. It is demonstrated that the charge transport is developed in a two-dimensional regime, proving that the minimum organic material needed to form the conductive channel scales well below a 10 nm organic layer thickness. Additionally, the Raman bands assignments are based on density functional theory (DFT) calculations. The chapter is concluded with a proposed model to describe the drain current relaxation during operation of the OFET device. In chapter 7, the influence of electric fields and illumination on the structural and transport properties of the OFET channel is discussed. The results are complemented with DFT calculations. In chapter 8, the intrinsic and field induced traps at the organic channel of OFET devices are investigated by QTS measurements. Additionally, the anomalous behavior of the QTS signal is experimentally demonstrated and analyzed by a proposed theoretical model. Finally, concluding remarks and a summary of this research are given in chapter 9.

References

“Organic field-effect transistors V”, edited by Z. Bao and D. J. Gundlach, Proc. SPIE 6336, Washington 2006. D. F. Barbe and C. R. Westgate, “Bulk trapping states in β -phthalocyanine single crystals”, J. Chem. Phys. 52, 4046-4054 (1970). D. F. Barbe and C. R. Westgate, “Surface state parameters of metal-free phthalocyanine single crystals”, Phys. Chem. Solids 31, 2679-2687 (1970). “Physics of organic semiconductors”, edited by W. Brütting, phys. stat. sol. (a) 201, 1037-1371 (2004).

[Ches2004] R. J. Chesterfield, J. C. McKeen, Ch. R. Newman, P. C. Ewbank, D. A. da Silva Filho, J. L. Brédas, L. L.

Miller, K. R. Mann, and C. D. Frisbie, “Organic thin film transistors based on N-alkyl perylene diimides:

charge transport kinetics as a function of gate voltage and temperature”, J. Phys. Chem. 108, 19281-19292

[Bao2006]

[Barb1970]

[Barb1970]

[Brüt2004]

(2004).

[Fiel1957] P. E. Fielding and F. Gutman, “Electrical properties of phthalocyanines”, The J. Chem. Phys. 26, 411-419

(1957).

[Hadz2000] “Semiconducting polymers: Chemistry, physics and engineering”, edited by G. Hadzüoannou and P. F. van Hutten, Wiley-VCH, Weinheim 2000. [Heeg2001] A. J. Heeger, “Nobel lecture: Semiconducting and metallic polymers: The fourth generation of polymeric materials”, Rev. Mod. Phys. 73, 681-700 (2001). [Heil1962] G. H. Heilmeier and G. Warfield, S. E. Harrison, “Measurement of the Hall effect in metal-free phthalocyanine crystals”, Phys. Rev. Lett. 8, 309 - 311 (1962).

H. E. Howe, “The electrical conductivity of fluorescent Anthracene vapor”, Phys. Rev. 30 (series I), 453-459

[Howe1910]

(1910).

[Hude2002] R. Hudej, and G. Bratina, “Electronic transport in perylenetetracarboxylic dianhydride: the role of In diffusion”, J. Vac. Sci. Technol.A 20, 797-801 (2002). [Hude2003] R. Hudej, and G. Bratina, “Electrical conductivity in metal/3,4,9,10-perylenetetrcarboxylic dianhydride structures”, J. Appl. Phys. 93, 6090-6094 (2003). [Kafa2005] “Organic light-emitting materials and devices IX”, edited by Z. H. Kafafi and P. A. Lane, Proc. SPIE 5937, Washington 2005. [Kahn2003] A. Kahn, N. Koch, W. Gao, “Electronic structure and electrical properties of interfaces between metals and

π -conjugated molecular films” , J. Pol. Sci. Part B: Pol. Phys. 41, 2529 – 2548 (2003). J. Kalinowsky, “Organic light-emitting diodes, principles, characteristics and processes”, Marcel Dekker, New York 2005.

[Kali2005]

Chapter 1. B. A. Paez-Sierra, Introduction

1.5

[Klau2006] “Organic electronics”, edited by H. Klauk, Wiley-VCH, Weinheim 2006.

[Klei1998]

Ch. Kleint, “Julius Edgar Lilienfeld: Life and profession”, Prog. Sur. Sci., 57, 253-327 (1998).

[Koba2003] S. Kobayashi, T. Takenobu, S. Mori, A. Fujiwara, Y. Iwasa, “C 60 thin-film transistors with high field-effect mobility, fabricated by molecular beam deposition”, Science and Technology of Advanced Materials 4, 371– 375 (2003). [Komm1961] J. Kommandeur and Frances R. Hall, “Electronic conduction in complexes of aromatic hydrocarbons with Iodine”, J. Chem. Phys. 34, 129-133 (1961). [Mann1949] D. E. Mann and J. R. Platt, “Spectral resemblances in azulene and naphthalene”, J. Chem. Phys., 17, 481-484

(1949).

[Nich1904] E. L. Nichols and E. Merrit, “Studies of luminescence. IV. The influence of light upon the absorption and electrical conductivity of fluorescent solutions”, Phys. Rev. 19 (series I), 396-421 (1904). [ofet] Schwerpunktprogramm 1121: Organische Feldeffekt-Transistoren: strukturelle und dynamische Eigenschaften www.ofet.de.Coordinator Prof. Dr. Christof Wöll. Activity in Chemnitz coordinated by Prof. Dr. D.r. h.c. D. R. T. Zahn and Dr. R. Scholz under the reference Za 146/4-2 as part of SPP 1121: Organic field effect transistors: Structural and dynamical properties. [Ostr1997] J. R. Ostrick, A. Dodabalapur, L. Torsi, A. J. lovinger, E. W. Kwock, T. M. Miller, M. Galvin, M. Beggren, and H. E. Katz, “Conductivity-type anisotropy in molecular solids”, J. Appl. Phys. 81, 6804-6808 (1997). [Paez2003] B. A. Paez, G. Salvan, R. Scholz, T. U. Kampen, and D. R. T. Zahn, “Interaction of metals with perylene derivatives as a model system for contact formation in OFET structures”, Proc. SPIE Int. Soc. Opt. Eng. 5217, 210-217 (2003). [Pari1956] R. Pariser, “Theory of the electronic spectra and structure of the polyacenes and of alternant hydrocarbons”, J. Chem. Phys., 24, 250-268 (1956). [Pope1999] M. Pope and C. E. Swenberg, “Electronic processes in organic crystals and polymers”, University Press, Oxford, second edition, 1999. [Regn1903] Regner, Physikalische Zeitschrift, 4, 862, (1903). [Reic2005] E. Reichmanis, H. Katz, C. Kloc, A. Maliaka, “Plastic electronic devices: From materials design to device applications”, Bell Labs Technical Journal 10, 87-105 (2005). [Salv2003] G. Salvan, “Metal/Organic/Inorganic semiconductor heterostructures characterized by vibrational spectroscopies”, PhD thesis, http://archiv.tu-chemnitz.de/pub/2003/0109/index.html TU Chemnitz 2003. [Scot2003] J. C. Scott, “Metal-organic interface and charge injection in organic devices”, J. Vac. Sci. Technol. A 21, 521–531 (2005). [Some2005] T. Someya, Y. Kato, S. Iba, Y. Noguchi, T. Sekitani, H. Kawaguchi, and T. Sakurai, “Integration of organic FETs With organic photodiodes for a large area, flexible, and lightweight sheet image scanners”, IEEE TRANSACTIONS ON ELECTRON DEVICES 52, 2502-2511 (2005). [Thur2005] I. Thurzo, H. Méndez and D. R. T. Zahn, “Dielectric relaxation in a hybrid Ag/DiMe-PTCDI/GaAs device”. J. non crystal. Sol. 351, 2003-2008 (2005). [Toll1960] G. Tollin, D. R. Kearns, and M. Calvin, “Electronic properties of organic solids. I. Kinetics and mechanism of conductivity of metal-free Phthalocyianine”, J. Chem. Phys. 32, 1013-1019 (1960). [Xue2004] J. Xue and S. R. Forrest, Bipolar doping between a molecular organic donor-acceptor couple”, Phys. Rev. B 69, 245322 1-8 (2004). [Zahn2004] D. R. T. Zahn, G. Salvan, B. A. Paez, R. Scholz, “Interaction between metals and organic semiconductors studied by Raman spectroscopy”, J. Vac. Sci. Technol. A 22, 1482-1487 (2004). [Zahn2005] D. R. T. Zahn, G. Salvan, G. Gavrila, and B. A. Paez, “Chemistry and morphological properties of metal interfaces to organic semiconductors”, Adv. sol. sta. phys. 45, 313-324 (2005). [Zahn2006] D. R. T. Zahn, G. N. Gavrila, and M. Gorgoi, “The transport gap of organic semiconductors studied using the combination of direct and inverse photoemission”, Chem. Phys. 325, 99-112 (2006).

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.1

Chapter 2

Fundamentals of molecular structures and Raman spectroscopy

2.1 Aromatic molecules

The π conjugation is what makes many organic molecules attractive for electronic applications, i.e., organic light emitting diodes (OLEDs) [Kafa2005], solar cells [Kafa2005], and OFETs [Bao2006]. The present work is based on a particular branch of π -conjugated aromatic structures named arenes, with the benzene ring as their structural building block. Most worked out molecules in the arene family are acenes, consisting of planar arrangements of benzene rings and sharing two carbons between them. Pentacene is a prototype molecule of the acene group (cf. Figure 2.1(a)). The acene family can be

described by the formula

, n being the number of benzene rings constituting the molecule.

Another important arene sub-group is the perylene derivatives, with perylene, PTCDA, and DiMe- PTCDI some representative molecular structures of this sub-family (cf. Figure 2.1(b)).

C

4n

+

2

H

2n

+

4

of this sub-family ( cf. Figure 2.1(b)). C 4n + 2 H 2n + 4 (a)

(a)

this sub-family ( cf. Figure 2.1(b)). C 4n + 2 H 2n + 4 (a) (b)

(b)

Figure 2.1. Some representative molecules of the arene family. (a) APentacene and (b) Perylene derivatives. (*) Main structures investigated in the present research.

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.2

2.2. The benzene ring and π-electron delocalization

As an example of π orbitals conjugation, the benzene ring is considered. Its carbon skeleton is arranged in a regular hexagon with bond lengths of 1.4 Å being halfway between the typical

sp

2

sp

2

single-bond distance of 1.46 Å and the

sp = sp double-bond distance of 1.34 Å. Each

2

2

carbon atom is involved in

adjacent carbon atoms, thus describing the σ bonds presented in Figure 2.2(a). The fourth electron

takes up a

sp hybrid atomic orbitals bonding to the hydrogen atom and the two

2

p

z orbital, which is for the most part situated at right angles to the plane of the molecule

z orbitals are fairly extended in space and overlap to form a pair of π -

(cf. Figure 2.2(b)). These

electron clouds on each side of the plane of the molecule, as illustrated in Figure 2.2(c) [Bowe2002,

Care2004]

p

as illustrated in Figure 2.2(c) [Bowe2002, Care2004] p (b) Figure 2.2. σ− hybrids and π− molecular

(b)

Figure 2.2. σ−hybrids and π−molecular orbitals in benzene. a) Localized σ−orbitals, b) p z atomic orbital, and c) delocalised π−orbitals with highest densities above and below the plane ring. (Thanks to G. Gavrila).

(a)

(c)

The delocalized π -electrons can move freely inside the molecule and are, therefore, sometimes called the mobile electrons or the unsaturated electrons, because they result from unsaturated bonds. Through such mobile π−electrons, electrical perturbations are easily transmitted from one part of the molecule to another.

2.3. Organic semiconductor solid

Organic materials are distinguished from inorganic solids basically due to the weak electronic interaction between nearer molecules.

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.3

Thus, in a conglomerate of molecules forming the organic solid, the weak electron-electron interaction takes the form of a kind of band structure through the π orbitals [Ishii1999, Pire1974-1984], cf. Figure 2.3. The effective potential well of an electron is formed by the atomic nuclei and other electrons. The wells of the nuclei are merged in the upper part to form a broad well. Deep atomic orbitals are still localized in the atomic potential well (core levels), but the upper ones interact to form delocalised molecular orbitals (MOs). The outermost horizontal part of the potential well is the vacuum level (VL). The energy separations of the highest occupied MO (HOMO) and lowest unoccupied (LUMO) from the vacuum level (VL) are the ionisation potential (IP) and the electron affinity (χ) of the molecular solid, respectively. Since the molecules interact only by the weak Van der Waals interaction, the top part of the occupied valence states and the lower unoccupied states are usually localised in each molecule, with narrow intermolecular bandwidths (typically lower than 0.1eV) [Gutm1967, Kao1981]. Thus, the electronic structure of an organic solid largely preserves that of a molecule and the validity of usual band theory (which assumes itinerant electrons) is often limited [Duke1980]. The electronic structure in an organic solid is usually simplified and presented as the one depicted on the right side of Figure 2.2. The Fermi level is also indicated there, since electrons fill the energy levels following the Fermi statistics [Ménd2006].

energy levels following the Fermi statistics [ Ménd2006]. 2.4. Transport in organic materials Figure 2.3.

2.4. Transport in organic materials

Figure

2.3.

Molecular

states

of

an

organic

solid

[Ishii1999,

Ménd2006,

Pire1974-1984].

A charge transport in the organic semiconductor is developed through overlapping of π neighboring molecular orbitals. The transfer of charge from site to site in the organic solid is assisted by internal and external or libronic phonons. The electronic conductivity of organic materials does not fully follow the classical diffusion models, and the mobility, together with other kinetic coefficients, is thermally activated due to the phonon-assisted process. Accordingly, there is a need to introduce a model able to describe the hopping process.

The dynamics of charge carrier-phonon interaction in an organic solid is given by the Hamiltonian of a coupled fermion-boson system [Cruz1992, Well1996]:

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.4

ˆ ( + ) + ( ˆ ˆ + ˆ ) H =− t o
ˆ
(
+
)
+
(
ˆ
ˆ
+
ˆ
)
H =−
t
o ∑
+ cˆ
+
μ
+
h
ω +
1
b
b
+
i,
σ
j,
σ
j,
σ
i, σ
i,
σ
i,
σ
i, σ
2
i
i
(i,j) σ
i, σ
i
,
(2.1)
(
)(
ˆ
+
ˆ
)
+
ε
h ω
− 1
b
+ b
n
ph
i σ
i
i
i, σ
where
−t
o denotes the transfer amplitude (attractive interaction) between nearest neighbor pairs ( i, j ).

This quantity is given by the product between the ionization potential and the overlap integral. The

is the

operator

)

(

+

i, σ

annihilates (creates) an electron at the site i

with spin projection σ ,

μ i, σ

chemical potential and takes into account the mean number of particles at a given temperature, ω

denotes

i σ

=

i

the

+

bare

phonon

frequency,

ˆ

b

(

i

+

)

is

the

i

is the number operator (electrons), and

phonon

annihilation

(creation)

operator,

ε

nph

is the energy of the electron-phonon

coupling. The Hamiltonian given in eq. (2.1) is the modern idea of the pioneering version of the coupling between the electron and the lattice vibrations, leading to the formation of a composite particle named polaron and introduced by Fröhlich [Fröh1950-1954], and later on by Lee [Lee1952], and in a variational form with path integrals by Feynmann [Feyn1955]. From tight binding theory, it is found that the band gap is approximately four times the transfer amplitude. Based on this result, in chapter 5 the charge carrier density for a two dimensional charge carrier gas is determined. An interesting feature of the Hamiltonian in eq.(2.1) is that the last term also accounts for trap occupation, and the coupling between the excess charge carriers with the phonons. It is known that

(

ˆ ˆ

b

+ +

i

b i

)

⎝ ⎜

ω ⎞

h

⎟ ⎠

ph

2m

= ⎜

1/ 2

i ,

m ph

being the phonon effective mass and

(2.2)

i the phononic-spatial coordinate. From eq.(2.2) and the

last term of the previous Hamiltonian (eq.(2.1)), one finds the strength between the phonon and the excess charge carriers given by

ξ =

2 2 2m ω ε = ε ε , ph n − ph ph n
2
2
2m
ω ε
=
ε
ε
,
ph
n
ph
ph
n
ph
A

with A the maximum amplitude of the normal mode with energy

ε

ph

.

(2.3)

2.4.1. Some input parameters for the coupled electron-phonon system

In the present work it has been theoretically and experimentally proved by combined Raman spectroscopy and applied electric fields that the vibrations of pentacene layers forming the channel in

FETs (chapter 7) are affected, in particular those where the ring and C-H vibrations are involved. The

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.5

representative Raman region is between 1120 cm -1 - 1210 cm -1 , which amounts to energies ranging

modes, having

between 139 meV and 150 meV. The affected vibrations basically correspond to

A

g

in-plane vibrations of C-H bonds at the outer rings, and vibrations of C-H bonds parallel to the main axis of the molecule.

Table 1 summarizes some input parameters for the Hamiltonian in eq.(2.1). The quoted values are the force constants K determined from density functional theory (DFT) at the B3LYP/3-21G level in Gaussian 98 [Gaus1998]. These values are extracted after geometry optimization and calculations of the vibrational Raman and infrared spectra of the pentacene molecule.

The next quantity in the table is the average energy of the local phonons < ε > , which are affected

ph

by the external electric field; these quantities were extracted from experimental measurements of the Raman spectra in pentacene-based FETs, discussed in chapter 7. Afterwards, the third column of the

> . The next

table lists the maximum amplitude (A) of the normal modes with average energy < ε

ph

column is the energy of the electron-phonon coupling

approximately the experimental activation energies

< ε

nph

>

; here the < ε

nph

>

is assumed to be

ε act

described in chapter 8. Finally, the last

column is the electron-phonon coupling ( ξ ) computed by means of the relation given in eq.(2.3).

Table 2.1. Parameters of the electron-phonon coupling in pentacene-based FETs.

K

<ε >

ph

A

ε

n

ph

≈ε

act

ξ

/ eV- Å -2

/ meV

/ Å

 

/ meV

/ eV- Å -1

172.45

143.0

0.04

25.0

 

2.9

167.1

 

7.60

127.25

146.3

0.05

25.0

 

2.51

167.1

 

6.49

2.4.2. Field effect mobility

The organic-semiconducting solid is characterized by a charge transport with low mobilities in conjunction with the monocrystalline or polycrystalline inorganic semiconductor. Usually, in most of the cases, the mobility is lower than that of the organic-crystal form. The charge transport is accompanied by thermally activated and electric-field dependent processes. Therefore, the charge transport model given by the coupled fermion-boson system in eq. (2.1) is well complemented by descriptions taking into account the explicit thermally activated and field dependent processes, i.e.,

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.6

Poole-Frenkel [Gill1972], disorder formalism [Bäss1981-2000], and multiple trapping and release

processes [Nool1977].

A model that might summarize most of the features stated in the previous descriptions is the “variable

hopping range” (VHR) by Vissenberg and Matters [Viss1998]. The VHR model predicts a thermal-

activated and gate voltage dependent mobility of the OFET device.

μ

eff

=

σ ⎡

πς

3

ς

(C V )

s

g

2

o

e

~

(2 α

3

) B

c

Γ −ς Γ +ς

(1

1

)

(1

1

)

2k

B

T ε

o

org

ς− 1

,

(2.4)

here

σ

o

~

is a prefactor, e is the electron charge, α

is the effective overlap between hopping sites,

B

c

gives the percolation criterion of the organic layer,

ς=

function. The thermal energy k T is below the width

B

k

T o

T o
T o

B

o

T

/ T

,

Γ

(x)

=

0

t

x

1

e

x

dx

is the gamma

of the exponential distribution of the

DOS, and the terms

C

s

,

V ,

g

ε

org correspond to the gate-dielectric capacitance per unit area, gate

voltage, and the dielectric constant of the organic material, respectively.

Considering a drop potential through the insulating dielectric layer and leaving eq.(2.4) as a simpler

power in dependence with the gate voltage, the drop potential yields [Meij2002]

μ eff

(

= μ V V

o

g

T

)

k

,

(2.5)

with

(ς − 1) in eq.(2.4). A typical value of the mobility in a-Si is about 1.1 cm 2 V -1 s -1 comparable with the hole mobility in several thin film organic-based transistors.

μ

o

the none-field dependent mobility,

V

T

the threshold voltage, and k an exponent given by

The thermally-activated field effect mobility, based on the Bolttzmann statistics and with a single trap

state following an exponential distribution, is proportional to [Ches2004]

μ eff

Sexp

ε

act

k

B

T

,

the factor S a fitting parameter.

(2.6)

If the material is free of traps, then the field effect mobility is described as

This power dependence is produced via scattering of charge carriers with phonons. When the

temperature increases, the exponent m has been found to increase for holes and decrease for electrons.

Experimental results have shown larger mobilities for holes than for electrons. On the other hand, if

the organic solid has a relative trap concentration c, the mobility is given by [Wolf1997]

μ

eff

T

m

being 1m4.

μ

eff

(c, T)

= μ

eff

(c

=

0, T)

1

+

⎛ ε

t

k

B

T

c exp

⎞ ⎤

1

,

(2.7)

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.7

the first factor accounts for the mobility without traps, and the second one is the trapping factor. Results presented in eqs.(2.4-2.7) are a fairly good estimate of the mobility. Those models are lacking

a

evidenced by Gomes et al. [Gome2004], and in this work has been proved by the correlated fitting of the output characteristics in OFETs (chapter 5), and by calculation of the time-dependent capture cross section based on QTS measurements (chapter 8).

description of the field dependence of threshold voltage ( V ). This has been experimentally

T

Additionally, field-dependent QTS measurements on OFETs with open gate configuration (chapter 8) proved that the trapping mechanism has several components which depend on the way the organic material is bias-pulsed. Although the gate-dielectric/organic interface is affected by traps, the applied electric field induces additional trapping sites in the organic material (chapters 5-8). Therefore, the conductive channel itself and likewise its boundaries, i.e., electrodes, bulk organic material, should not be excluded from the trapping phenomena.

2.5. Light-matter interaction 2.5.1. Raman spectroscopy

The interaction between photons and matter has gained an important position, fueling pure research and applications at different industrial levels. Among the optical techniques, Raman spectroscopy

plays a very important role in determining the vibrational properties of matter. The vibronic spectrum

is a fingerprint of each substance. Indeed, any physical or chemical alteration of the investigated

structure modifies its vibrational spectrum. The previous section addressed the importance of phonon-

assisted processes of charge transport in organic semiconductors.

Historically, the Raman effect was predicted by Smekal [Smek1923] in 1923 and the first experiment was performed by Sir C. V. Raman in 1928 [Rama1928]. Since then, innumerable experiments in diverse research fields, i.e., physics, chemistry, astronomy, biology, and many others, have been realised. Two years after the experimental discovery by C. V. Raman, an article by D. H. Andrew about the Raman spectra in organic molecules and the relation between the involved atoms and the formed bond nature [Andr1930] was reported, which can be considered as pioneering research in the vibrational molecular branch.

The usefulness of the method is mainly due to its sensitivity and non-destructiveness. It is capable of providing information on chemical identity [Gloc1943, Schm2006, Kuzm1988], charge states [Auss1986, Fleu1967, , Shan1972], processes at interfaces [Mile2006, Paez2003-2004, Zahn2001],

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.8

and structural order in organic materials [Colo2003], among many other interesting molecular features. Raman spectroscopy [Berm1988, Brig1980, Kuzm1988, Schü2006, Sing2005] is based on the inelastic interaction between light and matter. When light is scattered by any form of matter, the energies of the majority of the photons are unchanged by the process, corresponding to elastic or Rayleigh scattering. A minor number of photons, approximately one per million, are involved in the inelastic scattering process of creation (Stokes process) or annihilation (anti-Stokes process) of excitations within the medium. Therefore, the scattered photons will have an energy lower (Stokes) or higher (anti-Stokes) than that of the incident light. Most routine Raman experiments use the red- shifted Stokes peaks, because they are more intense at room temperature.

peaks, because they are more intense at room temperature. Figure 2.4. Spectrum of scattered light showing

Figure 2.4. Spectrum of scattered light showing the Raman Stokes, Rayleigh, and Raman anti-Stokes bands.

Figure 2.4 shows the Stokes, Rayleigh, and anti-Stokes processes, where a photon with energy

hω

exc

and momentum

k exc

is scattered by the creation or annihilation of an elementary excitation with

energy

hω

i

and momentum

q . The scattered photon has an energy h ω′ and momentum

i

k

exc

. This

means each scattered photon in the Stokes component is associated with a gain in energy

hω

i

by the

sample. Similarly, the sample loses energy

component.

hω

i for each scattered photon in the anti-Stokes

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.9

The conservation energy reads:

hω′ = hω ± hω ,

exc

i

(2.8)

where the minus (plus) sign is for the Stokes (anti-Stokes) process. Conservation of momentum requires

k ′ = k ± q ,

exc

i

(2.9)

Here, the plus (minus) sign is for the Stokes (anti-Stokes) process. Schematically, a Raman spectrum

with energy

hω looks like that displayed in Figure 2.4. There is a very strong component due to

i

elastic scattered photons, i.e., with energy

hω .

exc

In chapter 3, the experimental Raman setup used during this investigation to characterize the vibrational bands of organic / inorganic interfaces (chapter 4) and OFETs (chapters 6-8) is discussed.

2.5.2. Basic theoretical background on Raman spectroscopy 2.5.2.1. Classical description of the Raman effect

Classically, Raman scattering can be explained by molecular polarizability ( α ) modulation. When a

)

molecule is subjected to the electric field

E

=

l

E

o

exp(j

ω

l

t)

of

a

multi-energetic

(

hω

l

 

(2.10)

electromagnetic beam, its dipole moment μ is given by

(0)

μ=μ +αΕ

,

the induced dipole moment by the electric field Ε ,

and α the polarizability, which can be expressed by the superposition due to elastic (Rayleigh) and inelastic (Raman) contributions

, with the first term on the right hand side being the induced-Rayleigh polarizability and the second the Raman induced polarizability.

with

μ

(0)

the permanent dipole and

μ

(ind)

= α Ε

α = α

(Rayleigh)

+ α

(Raman)

(2.11)

The matrix form of eq.(2.10) in Cartesian coordinate is written as follows:

⎡ μ ⎤

x

μ

μ

y

z

⎡ μ ⎤

(0)

x

(0)

y

(0)

z

= μ

μ

⎡ α ⎢ + ⎢ α ⎢ ⎣

α

x

y

z

x

x

x

α

x y

α

y y

α

z y

α

x z

α

y z

α

z z

⎤ ⎡ E

E

E

x

y

z

.

(2.12)

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.10

The character of the polarizability tensor depends on the symmetry of the molecule. On the other hand, it must be noted that the dipole moment and the electric field do not necessarily share similar unit vectors (sect. 8.8). Since Ε is a frequency dependent electric field, the coordinates of the atoms might be affected.

Therefore, instead of specifically using the atom position, the normal coordinates q (t)

are

considered. The number of normal coordinates equals the total number (N) of vibrational modes. For

small vibrations, q (t)

i

can be approximated by

i

q (t)

i

where

=

q

q

o

cos(

ω

i

t)

,

o is the maximum amplitude and

(2.13)

ω i is the vibrational frequency of i-th normal mode.

Assuming a monochromatic light source ( l = 1) to excite the sample, and expanding the polarizability in terms of the normal coordinates, the total dipole moment is then given by:

coordinates, the total dipole moment is then given by: , (2.14) where the different contributions to

,

(2.14)

where the different contributions to the induced dipole moment are commented on in the equation, the term O(3) meaning third order derivatives. For the present research, only terms up to first order

, then the corresponding -i-th- mode will not appear in the

derivatives are considered. If

⎛ ∂α

q

i

0

= 0

Raman spectrum. A similar situation occurs for the infrared spectrum if

⎛ ∂μ

q

i

0

= 0

. It has been proved

that if the molecule has an inversion center of symmetry, the Raman active modes are not observed in infrared, and those active in infrared will be absent from the Raman spectrum.

2.5.2.2. Quantum mechanical description of the Raman effect

The classical theory correctly predicts the frequency dependence for Rayleigh scattering and vibrational Raman scattering. It also shows correctly the dependence of the Rayleigh scattering tensor

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.11

( α ). On the other hand, the classical description has some limitations. It cannot be applied to

) of the Raman scattering tensor

molecular rotations. The result for the induced polarizability ( α is only partly correct.

is related to the properties

of the molecule, in particular its characteristic transition frequencies, or to the frequency of the incident radiation. Fortunately, the quantum mechanical model provides this information and bridges the gap from the classical description to a complete treatment of all aspects of Raman scattering

[Long2002].

The electric dipole moment ( μ ) given in eq.(2.10) can vary, due to the dynamics of the atomic motifs

comprising the molecule; consequently, vibronic transitions at any electronic state are expected. As an example, in Figure 2.5(a) the vibronic energy levels of a diatomic molecule are depicted with the wave functions on the intemolecular Morse potential, and are distributed for each electronic state with energy E e and the associated quantum numbers, i.e., principal (n), angular (j), orbital (l) and magnetic

. The

likely vibronic transitions at this electronic level are summarized by the infrared transitions shown in Figure 2.5(b). Another process is developed when the electronic state remains unmodified, thus the transitions are developed between tne vibrational levels at the electronic ground state. If the scattered photon has the same energy as the incoming radiation, the process is named Rayleigh scattering (cf. Figure 2.7(a)).

(Rayleigh)

(Raman)

The classical picture does not provide information about how the

α (Raman)

~

( m

). Each vibrotional state is characterized by a frequency

ω

i

and normal coordinate modes

q

i

by a frequency ω i and normal coordinate modes q i (a) ( b ) Figure

(a)

by a frequency ω i and normal coordinate modes q i (a) ( b ) Figure

(b)

Figure 2.5. Molecular Morse potential of the (a) ground electronic and bound vibrational states. (b)

Infrared activity described by transitions between vibrational states at a given electronic state

E n jlm

e

.

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.12

Otherwise, the normal Raman scattering is achieved and described by the Stokes (cf. Figure 2.6(b)) and anti-Stokes (cf. Figure 2.6(c)) scattering. There is an extension of the previous description when the excitation energy is comparable to that of the first excited electronic state or above; then similar scattering phenomena are developed, where the excitation attains the manifold electronic states and consequently the resonant Raman effect is achieved as described in Figure 2.7. It can be deduced from Figure 2.7 that the Raman bands (transitions) are most intense when the wave function of the upper vibronic state resembles that of the ground state of the vibrational wave function. The amplitudes of these vibronic transitions are proportional to the square of the probability of the

corresponding initial (

) electronic excited vibronic states [Fran2000,

jn;r

o

g

) and final (electronic excited vibronic states [Fran2000, jn;r o − g ′ j m;r o − e Joha2005]. electronic excited vibronic states [Fran2000, jn;r o − g ′ j m;r o − e Joha2005].

j m;r

o

e

[Fran2000, jn;r o − g ) and final ( ′ j m;r o − e Joha2005].

Joha2005].

jn;r o − g ) and final ( ′ j m;r o − e Joha2005]. (a)

(a)

o − g ) and final ( ′ j m;r o − e Joha2005]. (a) (b)

(b)

o − g ) and final ( ′ j m;r o − e Joha2005]. (a) (b)

(c)

Figure 2.6. Non-resonant Raman effect involving (a) elastic light scattering or Rayleigh scattering, and the inelastic processes: (b) Stokes scattering with the scattered photon energy higher than the incoming one, and (c) anti-Stokes where the scattered photon possesses lower energy than that of the excitation source.

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.13

In this scheme the vibronic wave function ( (r ) ) of the Morse potential
In this scheme the vibronic wave function (
(r )
) of the Morse potential is described by
ψ j,n
o
2n!
β
(j
n)
j
n
2 j
2 n
ψ
(r
)
=
r
j n
=
exp(
−ξ
/ 2)
ξ
L
(
ξ
)
,
(2.15)
j,n
o
o
n
Γ
(2 j
− +
n
1)
2 j
− 2 n
with
ξ=
(2 j
+
1) exp(
−β
r o )
,
L
( ξ )
the associated Legendre polynomials, and the bonding
n

energy of the state

jn

expressed as

E

n

= −(β h / 2

2

2

~

m)( j

n)

2

. The amplitude is proportional to

the transition

; jn r ; j′m r o − g o − e
; jn r
; j′m
r o
g
o
e

2

, which can be readily integrated to determine the overlap

between vibronic states. Note that as long as the difference of the minimum position between the non- excited and excited states is small, the vibrational transition probability increases. This is attributed to allowed dipole transitions.

This is attributed to allowed dipole transitions. Figure 2.7. Resonant Raman effect (a) vibronic transitions

Figure 2.7. Resonant Raman effect (a) vibronic transitions pointing to the Raman-Stokes, Raman-anti-Stokes, and Rayleigh scattering.

For a molecular structure, those states are mainly between HOMO and LUMO. The intensity of the

Raman scattered light with polarization ρ of the excitation light is given by [Garo1976, Kürt1991]

2 4 I ∝ I ω ρ o σ f α ρσ
2
4
I
I
ω
ρ
o
σ
f
α ρσ

,

(2.16)

where

I

oσ

is the intensity of the incoming light with polarizability σ , and inelastically scattered with

frequency

ω

f

. The polarizability in this frame is described in the form [Hass2004]:

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.14

~ ~ ~ ~ ⎡ ⎤ f μ ˆ f f μ ˆ g f
~
~
~
~
f μ
ˆ
f
f
μ
ˆ
g
f
μ
ˆ
f
f
μ ˆ
g
ρ
σ
σ
ρ
α
=
+
,
(2.17)
ρσ
~
⎢ (E
E
)
− ω
h
i
h
Γ
(E
E
)
+ h ω
+
i
h
Γ
~
~
~
~
f
f
g
exc
f
f
f
exc
f
where
μˆ
is the electric dipole operator and takes into account the electronic and nuclear
ρσ
~
contributions. The states
f
,
f
,
and
g
denote the final, intermediate, and initial states,

respectively. The corresponding energies are

E

f

,

coefficient. If the energy of the incident radiation ( h ω

(E

~

f

E

g

)

, then the interaction will be in resonance.

E~ ,

f

and

E~ . The factor

g

Γ~

f

is a damping

exc

) approaches the molecular transition energy

The efficiency of the Raman signal is measured by the photon-scattering cross section [Joha2005]

3 ω′ω f (1,n)f (0,n) 4 exc = p σ RS o 2 4 ∑
3
ω′ω
f (1,n)f (0,n)
4
exc
= p
σ RS
o
2
4
∑ h
6
πε
ω
n
h
ω
− h Ω
+
i
h
Γ
o c
n
exc
vib
ge
tot
with
ω′ = ω
− ω
,
exc
vib
Γ
=
γ + γ
/ 2
+ γ
/ 2
,
tot
ph
vib
rad,0

2

,

(2.18)

(2.19)

(2.20)

γ : interaction with the vacuum fluctuations expressed by Fermi’s golden rule

rad,0

γ : dephasing rate

rad,0

h Ω

ge

: energy level separation

p

o

= e l

dip

: dipole with elementary charge e and length

l

dip

Ω vib

corresponds to the pure vibrational frequencies of the associated harmonic Hamiltonian

The typical order of σ

RS

is about

10

29

cm

2

. The next section describes the procedure for enhancement

of the Raman signal. It involves the magnification of the cross section.

2.5.3. Surface-enhanced Raman scattering (SERS)

In the previous section, it was pointed out how small the Raman signal is in comparison to the intensity of the incoming excitation laser energy. In order to enhance the detected Raman spectrum intensity, several technological efforts have been targeted at circumventing this detection limit.

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.15

An interesting phenomenon which developed locally in the tested sample is observed when the material is embedded in a metal-matrix environment. Although a perfect metal surface behaves as a mirror for the electromagnetic radiation, this can be avoided by texturing the surface in a way that the patterned layer will no longer be a quasi or perfect reflector for the light. Indeed, the modified surface geometry substantially enhances the local electric field. The resulting local field produced in the clusters is much higher, then the material in the vicinity is electronically and structurally altered by the

(ind)

field, therefore, parallel signatures are induced, organic electric dipole ( μ ) coupling with the

metallic cluster plasmon, molecular polarizability ( α ω ), and charge transfer (CT) (cf. Figure

(Raman)

(

)

2.8) among others. The Raman signal is enhanced, usually by several orders of magnitude. The phenomenon is referred to as surface-enhanced Raman spectroscopy SERS [Aroc2006, Mosk2002].

Raman spectroscopy SERS [Aroc2006, Mosk2002]. Figure 2.8. Examples of SERS from a (a) pentacene (30

Figure 2.8. Examples of SERS from a (a) pentacene (30 nm)-based OFET, and a (b) In (15 nm)/ PTCDA (15 nm)/S-GaAs heterostructure.

The SERS signal is divided into two principal contributions, one from the interface formed between the first molecular layer and the metal, called chemical enhancement or first layer effect. The other one is a long-range contribution mediated by the huge local electric field, referred to as electromagnetic enhancement.

The magnification factors (based on this research) are estimated to be 10 1 -10 2 for the chemical contribution or first monolayer effect [Pers2006], and 10 2 or higher for the electromagnetic contribution. Therefore, the cross sections are magnified from ca. 10 -29 cm 2 to 10 -17 -10 -14 cm 2 [Joha2005, Knei1997, Otto2001]. Due to this pronounced enhancement of the photon cross section,

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.16

SERS is widely used in analytical science and technology [Aroc2006, Cao2005, Mosk2002, Vo2004]. Detailed theoretical descriptions about SERS are found elsewhere [Aroc2006, Joha05, Knei1997, Otto2001, Pers2006]. As an example, figs. 2.9(a) and 2.9(b) illustrate the Raman spectra of a pentacene (30 nm) layer forming the channel in an OFET structure. It should be noted that the Raman signal of molecules on the gate dielectric is much lower that that produced by molecules deposited on the Au electrodes; the enhancement factor for this experiment was about 31. The panel given in Figure 2.8(b) consists of the Raman spectra from bare PTCDA (15 nm) deposited on S-GaAs and an In layer of 15 nm deposited on the previous structure; the Raman bands are enhanced by a factor of about 10 2 . The metallic overlayer produces a breakdown of the molecular symmetry, since the activated modes were originally infrared active modes of the bare molecular layer. Additionally, a well-defined charge transfer (CT) is developed. It can be observed that both structures, pentacene (30 nm)-based OFET and In/PTCDA, have a markedly different base line, depending on whether the molecular layer is on the inorganic substrate or is interfacing with the metal electrode.

2.5.4. Combined Raman spectroscopy with electric fields

The application of an electric field affects the optical absorption and the scattering of electromagnetic (EM) radiation by optical phonons; both have been observed in inorganic semiconductors and aromatic molecules [Auss1986, Fleu1967, Shan1972]. These changes result from several effects of the modulating field: First it lifts the degeneracies of both the phonon and the electronic states, and second it affects the symmetries of the corresponding wave functions. As a consequence, the Raman-active phonon modes can shift energetically, and, due to changes of the selection rules, new scattering transitions can contribute to the Raman signal. When an external electric field is applied to a molecule, the electronic charges are redistributed between different atomic sites, resulting in induced dipole moments; therefore, the energy potential described in section 2.5.2.1 is distorted. Thus the Frank- Condon transitions are subjected to the new molecular organization, provoking changes in the Raman cross section.

In chapter 7, the experimental results of the Raman signal with applied electric fields in organic-based field effect transistors (OFETs) are described. Moreover, it is theoretically described how the applied field (E) in a given direction produces modifications of the molecular dipole moment, resulting in effective contributions that in general do not follow the direction of the field (eq. (2.12)). The nature of the applied field can be a time dependent or a static perturbation. Both fields were applied to the OFETs (chapter 6-8). In addition, in chapter 7, the experimental and theoretical measurements of combined Raman spectroscopy with electric fields and the effect on the structural properties of the pentacene layer in OFETs are described. Furthermore, after the removal of the

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.17

applied bias, the molecular layer follows a relaxation process, which was demonstrated by the Raman bands relaxation. The decay time was confirmed by charge transient spectroscopy (QTS), revealing novel phenomena never seen in pentacene-based FETs [Thur2006], addressed by the authors as “anomalous QTS”. On the other hand, the calculated cross sections from QTS are comparable with the photon cross section, due to chemical enhancement in SERS. From both techniques, it has been inferred that the application of the electric field induces electric dipole states at the organic material. The theoretical simulations of the vibronic properties in the present investigation were done within the framework of the density functional theory (DFT), using the package Gaussian 98 [Gaus1998] at the B3LYP level [Beck1993] with 3-31G basis sets having Gaussian-like wave functions [Helg2000]. The fundamentals of the DFT are reported in detail elsewhere [Koch2002, Parr1989].

References

[Andr1930]

D. H. Andrews, “The relation between the Raman spectra and the structure of organic molecules”, Phys. Rev.

36, 544-554 (1930). [Auss1986] F. R. Aussenegg and M. E. Lippitsch, “On the electric field dependence of Raman scattering”, J. Raman Spectrosc. 17, 45-49 (1986).

[Aroc2006]

R. Aroca, “Surface-enhanced vibrational spectroscopy”, Wiley, Chichester, 2006.

[Bao2006] “Organic Field-Effect transistors V”, edited by Z. Bao and D. J. Gundlach, Proc. SPIE 6336, Washington

2006.

[Bäss1981] H. Bässler, “Localized states and electronic transport in single component organic solids with diagonal

disorder”, phys. stat. sol. (b) 107, 9-54 (1981) “Charge transport in random organic semiconductors” in “Semiconducting polymers: Chemistry, physics and engineering”, chap. 12. Edited by G. Hadzüoannou and P. F. van Hutten, Wiley-VCH, Weinheim 2000.

[Bäss2000]

[Beck1993] A. D. Becke, “Density-functional thermochemistry. III. The role of exact exchange”, J. Chem. Phys. 98, 5648–5652 (1993).

[Berm1988]

D. Bermejo, “Itroduction to Raman spectroscopy”, OEA, Spain, 1988 (in spanish).

[Bowe2002]

D. I. Bower, “An introduction to polymer physics”, Cambridge University Press, UK 2002.

[Brig1980] E. B. Wilson, Jr., J. C. Decius and P. C. Cross, “Molecular vibrations: The theory of Infrared and Raman Vibrational Spectra”, Dover publications, Inc. New York, 1980.

[Cao2005]

L. Cao, P. Diao, L. Tong, T. Zhu, and Z. Liu, “Surface-enhancement Raman scattering of p-Aminothiophenol

[Care2004]

on a Au(core) / Cu (shell)”, Chem. Phys. Chem. 6, 913-918 (2005). F. Carey, “Organic chemistry”, 5 th Edition, The McGraw-Hill Co., 2004.

[Ches2004] R. J. Chesterfield, J. C. McKeen, Ch. R. Newman, P. C. Ewbank, D. A. da Silva Filho, J. L. Brédas, L. L.

Miller, K. R. Mann, and C. D. Frisbie, “Organic thin film transistors based on N-alkyl perylene diimides:

charge transport kinetics as a function of gate voltage and temperature”, J. Phys. Chem. 108, 19281-19292

(2004).

[Colo2003] P. Colomban, “Raman analysis and smart imaging of nanophases and nanosized materials”, Spectroscopy Europe 15 (6), 8-16 (2003).

[Cruz1992]

M. G. Cruz, “Path integral approach to the small polaron model in the atomic limit”, Am. J. Phys. 60, 1127-

[Duke1980]

1131 (1992). C. B. Duke and L. B. and Schein, “Organic solids: is energy-band theory enough?”, Phys. Today. 33, 42-48

(1980).

[Feyn1955]

R. P. Feynman, “Slow electrons in a polar crystal”, Phys. Rev. 97, 660-665 (1955).

[Fleury1967] P. A. Fleury and J. M. Worlock, “Electric-field-induced Raman effect in paraelectric crystals”, Phys. Rev.

[Fran2000]

Lett. 18, 665 - 667 (1967). A. Frank, A. L. Rivera, and K. B. Wolf, “Wigner function of Morse potential eigenstates” ,Phys. Rev. A 61,

[Fröh1950]

054102 (2000). H. Fröhlich, H. Pelzer, and S. Zieuau, Philos. Mag. 41, 221 (1950).

[Fröh1954]

H. Fröhlich, “Electrons in lattice field”, Adv. Phys. 3, 325-361 (1954).

[Garo1976] M. Garozzo and F. Galluzzi, “A comparison between different approaches to the vibronic theory of Raman

intensities”, J. Chem. Phys. 64, 1720-1723 (1976).

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.18

[Gaus1998] Gaussian 98 (Revision A.1), M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G., Zakrzewski, J.A. Montgomery, R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A., Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M. W. Gill, B.G. Johnson, W. Chen, M.W. Wong,

J.L. Andres, M. Head-Gordon, E.S. Replogle and J.A. Pople, Gaussian, Inc., Pittsburgh PA, 1998. [Gill1972] W. D. Gill, “Drift mobilities in amorphous charge-transfer complexes of trinitrofluorenone and poly-n- vinylcarbazole”, J. Appl. Phys., 43, 5033-5040, (1972).

[Gloc1943]

G. Glockler, “The Raman effect”, Rev. Mod. Phys. 15, 111-173 (1943).

[Gome2004] H. L. Gomes, P. Stallinga, F. Dinelli, M. Murgia, F. Biscarini, D. M. de Leeuw, T. Muck, J. Geurts, L. W. Molenkamp, and V. Wagner, “Bias-induced threshold voltages shifts in thin-film organic transistors”, Appl. Phys. Lett. 84, 3184-3186 (2004).

[Gutm2004]

F. Gutmann and L. E. Lyons, “Organic semiconductors”. Wiley, N. Y. (1967).

[Hass2004]

S. Hassing and E. Nørby, “The correct form of the Raman scattering tensor”, J. Raman Spectrosc. 35, 87-90

(2004)

[Ishii1999] H. Ishii, K. Sugiyama, E. Ito and K. Seki, “Energy level alignment and interfacial electronic structures at organic/metal and organic/organic Interfaces” Adv. Mater. 11, 605-625 (1999). [Helg2000] T. Helgaker, O. Jørgensen, and J. Olsen, “Molecular electronic-structure theory”, (Hohn Wiley & Sons, England, 2000). [Joha2005] P. Johansson, H. Xu, M. Käll, “Surface-Enhanced Raman Scattering and fluorescence near metal nanoparticles” ,Phys. Rev. B 72, 035427 (2005).

[Kafa2005]

“Organic Light-Emitting materials and devices IX”, edited by Z. H. Kafafi and P. A. Lane, Proc. SPIE 5937,

[Kao1981]

Washington 2005. K. C. Kao and W. Hwang, “Electrical transport in solids”. Pergamon Press, Oxford (1981).

[Knei1997] K. Kneipp, Y. Wang, H. Kneipp, L. T. Perelman, I. Itzkan, R. R. Dasari, and M. S. Feld, “Single molecule detection using Surface-Enhanced Raman Scattering (SERS)”, Phys. Rev. Lett. 78, 1667–1670 (1997).

[Koch2002]

W. Koch, M. C. Holthausen. “A chemist’s guide to density functional theory”, Wiley-VCH, Germany, 2002.

[Kuzm1988]

H. Kuzmany, “Solid-State Spectroscopy, an introduction” (Springer-Verlag, Berlin Heidelberg, 1988).

[Kürt1991]

J. Kürti and H. Kuzmany, “Resonance Raman scattering from finite and infinite polymer chains”, Phys. Rev.

B

44, 597-613 (1991).

[Lee1952]

T. D. Lee and D. Pines, “The motion of slow electrons in polar crystals”, Phys. Rev. 88, 960 - 961 (1952).

[Long2002]

D. A. Long, “The Raman effect: A unified treatment of the theory of Raman scattering by molecules”, JOHN

WILEY & SONS, LTD, Chichester, 2002. [Ménd2006] H. Méndez, , “Organic modification of Metal / Semiconductor contacts”, PhD Dissertation, http://archiv.tu- chemnitz.de/pub/2006/0124/index.html TU Chemnitz (2006).

[Meij2002] E. J. Meijer, C. Tanase, P. W. M. Blom, E. van Veenendaal, B.-H. Huisman, D. M. de Leeuw, and T. M. Klapwijk, “Switch-on voltage in disordered organic field-effect transistors”, Appl. Phys. Lett. 80, 3838-

3840(2002).

[Mile2006] A. G. Milekhin, R. Meijers,T. Richter, R. Calarco, S. Montanari, H. Lüth, B. A. Paez-Sierra, and D. R. T. Zahn, “Surface enhanced Raman scattering by GaN nanostructures obtained by bottom-up and top-down approach”, J. Phys.Cond.Matt. 18, 5825-5834 (2006). [Mosk2002] M. Moskovits, Ll. Tay, J. Yang, T. Haslett, “SERS and the single molecule”, in “Optical properties of nanostructured random media”, Series: Topics in Applied Physics , Vol. 82, 215-226, Edited by Shalaev, Springer Berlin Vladimir M. 2002.

[Nool1977]

J. Noolandi, “Multiple-trapping model of anomalous transit-time dispersion in a-Se”, Phys. Rev. B 16, 4466-

[Otto2001]

4473 (1977). A. Otto, “Theory of first layer and single molecule surface enhanced Raman scattering (SRS)”, phys. stat. sol.

[Paez2003]

(a) 188, 1445-1470 (2001). B. A. Paez, M. Bartzsch, G. Salvan, R. Scholz, T. U. Kampen, and D. R. T. Zahn, “Combined electrical and Raman characterization of C 60 based organic field effect transistors”, Proc. SPIE Int. Soc. Opt. Eng. 5217, 63

(2003).

[Paez2003] B. A. Paez, G. Salvan, R. Scholz, T. U. Kampen, and D. R. T. Zahn, “Interaction of metals with perylene derivatives as a model system for contact formation in OFET structures”, Proc. SPIE Int. Soc. Opt. Eng. 5217, 210 (2003).

[Paez2004]

B. A. Paez, G. Salvan, S. Silaghi, R. Scholz, T. U. Kampen and D. R. T. Zahn, “Raman monitoring of In and

[Parr1989]

Ag growth on PTCDA and DiMe-PTCDI thin films”, Appl. Surf. Sci. 234, 168-172 (2004). R. G. Parr and W. Yang, “Density-functional theory of atoms and molecules”, (Oxford University Press, New

York1989).

[Pers2006] B. N. J. Persson, K. Zhao, and Z. Zhang, “Chemical contribution to surface-enhanced Raman scattering”,

[Pire1974]

Phys. Rev. Lett. 96, 207401 (2006). J. J. Pireaux, J. Riga, R. Caudano, J. J. Verbist, J. M. Andre, J. Delhalle and S. Delhalle, “Electronic structure

of

fluoropolymers : Theory and esca measurements”,J. Electron Spectrosc. Relat. Phenom. 5, 531-550 (1974).

[Pire1984]

J. J. Pireaux and R. Caudano, “Experimental picture of the band structure formation in a solid”, Am. J. Phys. 52, 821-826 (1984).

[Rama1928]

C. V. Raman and K. S. Krishnan, “A new type of secondary radiation”, Nature 121, 501–502 (1928).

Chapter 2 B. A. Paez-Sierra, Fundamentals of molecular structures…

2.19

[Schm2006] M. Schmitt and J. Popp, “Raman spectroscopy at the beginning of the twenty-first century, J. of Raman

Spectroscopy 37, 20-28 (2006). [Schü2006] C. Schüller, “Inelastic light scattering of semiconductor nanostructures, fundamentals and recent advances”, chap. 4., Springer Tracts in Modern Physics Volume 219, Berlin Heidelberg, 2006. [Shan1972] M. L. Shand, W. Richter, E. Burstein, and J. G. Gay, “Electric field induced Raman scattering in CdS”, J. Nonmmetals 1, 53-62 (1972). [Sing2005] A. Singha, P. Dhar, and A. Roy, “A nondestructive tool for nanomaterials: Raman and photoluminescence spectroscopy”, Am. J. Phys. 73, 224-233 (2005).

[Smek1923]

A. Semkal, “Zur Quantentheorie der Dispersion”, Naturwiss. 11, 873-875 (1923).

[Thur2006]

I. Thurzo, B. Paez, H. Méndez, R. Scholz, and D. R. T. Zahn, “Anomalous charge relaxation in channels of

[Viss1998]

pentacene-based organic field-effect transistors: a charge transient spectroscopy study”, phys. stat. sol. (a) 203, 2326-2340 (2006). M. C. J. M. Vissenberg, M. Matters, “Theory of the field-effect mobility in amorphous organic transistors”,

Phys. Rev. B 57, 12964-12967 (1998). [Well1996] G. Wellein, H. Röder, and H. Fehske, “Polarons and bipolarons in strongly interacting electron-phonon systems”, Phys. Rev. B 53, 9666–9675 (1996). [Wolf1997] U. Wolf, H. Bässler, P. M. Borsenberger and W. T. Gruenbaum, “Hole trapping in molecularly doped polymers”, Chem. Phys. 222, 259-267 (1997)

[Zahn2001]

D. R. T. Zahn, “Raman studies of molecular thin films”, phys. stat. sol. (a) 184, 41-50 (2001).

Chapter 3 B. A. Paez-Sierra, Experimental techniques…

3.1

Chapter 3

Experimental techniques, materials, and algorithms

In this chapter, the investigated molecular structures and the main experimental characterization techniques involved to scope the organic/inorganic structures are discussed. The most frequently used experimental methods to characterize the samples during this research were Raman spectroscopy, scanning Raman spectroscopy, current voltage (I-V) characteristics, and charge transient spectroscopy (QTS). The molecular structures consist of perylene derivatives named 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA) and 3,4,9,10- N-N’-dimethyl-3,4,9,10-perylenetetracarboxylic diimide (DiMe- PTCDI). These organic molecules were evaporated by molecular beam deposition (MBD) under UHV conditions and deposited on S-GaAs substrates. Indium or magnesium were deposited on these organic molecules and they were characterized in situ by surface-enhanced Raman spectroscopy (SERS) experiments. The organic molecules to form the active layer of the FET structures were pentacene and C 60 ; minor work was done on the C 60 –based devices. The data evaluation was carried out primarily in special routines written in MatLab [MATL2003], with a particular code based on a consistent recursivity of initial boundary conditions developed to achieve efficient data evaluation. Furthermore, in some theoretical modeling involving numerical integration, a routine based on the Gauss quadrature was constructed. As a result, high accuracy and convergence speed in comparison with standard geometrical integration methods were achieved.

3.1. Combined Raman spectroscopy and electrical characterization setups

In chapter 2, the fundamentals of Raman spectroscopy were given. In this section, the experimental setup used for this research is outlined. The Raman spectrometer employed during this work was a triple monochromator Dilor XY 800 model from Dilor. The system is equipped with a Peltier-cooled CCD (256x1024 pixels) camera for

Chapter 3 B. A. Paez-Sierra, Experimental techniques…

3.2

multichannel detection in a back scattering configuration geometry. This allows the setup to be used in macro- and micro-configuration.