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Absolute number density and kinetic analysis of CF, CF_1tn2 and C_1tn2_1tn4 molecules in pulsed CF_1tn4,H_1tn2 rf plasmas [Elektronische Ressource] / vorgelegt von: Sergey Stepanov

160 pages
ERNST{MORITZ{ARNDT{UNIVERSITATGREIFSWALDAbsolute number density and kinetic analysisof CF, CF and C F molecules in2 2 4pulsed CF /H rf plasmas4 2I n a u g u r a l d i s s e r t a t i o nzurErlangung des akademischen Gradesdoctor rerum naturalium (Dr. rer. nat.)an der Mathematisch{Naturwissenschaftlichen FakultatderErnst{Moritz{Arndt{Universitat Greifswaldvorgelegt von: Sergey Stepanovgeboren am 17. November 1980in Sankt{Petersburg (Russland)Greifswald, 26. April 2010Dekan: Prof. Dr. Klaus Fesser1. Gutachter: Prof. Dr. Jurgen Meichsner2. Gutachter: Prof. Dr. Uwe CzarnetzkiTag des Promotionskolloquiums: 09. Juli 2010ContentsAbbreviations iiiList of symbols vGeneral introduction 11 Fluorocarbon RF plasmas 51.1 Fluorocarbon plasmas and their applications . . . . . . . . . . . . . . 51.2 Capacitively coupled RF discharges . . . . . . . . . . . . . . . . . . . 71.3 Gas phase processes in uorocarbon plasmas . . . . . . . . . . . . . . 101.4 Reactive plasma{surface interaction . . . . . . . . . . . . . . . . . . . 151.5 Diagnostic methods for gas phase analysis in uorocarbon plasmas . . 171.6 Experimental techniques for uorocarbon thin lms characterization . 202 Basics on molecular spectroscopy 232.1 Structure of molecular spectra . . . . . . . . . . . . . . . . . . . . . . 232.1.1 Vibrational energy levels and transitions . . . . . . . . . . . . 242.1.2 Rotational energy levels and transitions . . . . . . . . . . . . . 272.1.
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ERNST{MORITZ{ARNDT{UNIVERSITAT
GREIFSWALD
Absolute number density and kinetic analysis
of CF, CF and C F molecules in2 2 4
pulsed CF /H rf plasmas4 2
I n a u g u r a l d i s s e r t a t i o n
zur
Erlangung des akademischen Grades
doctor rerum naturalium (Dr. rer. nat.)
an der Mathematisch{Naturwissenschaftlichen Fakultat
der
Ernst{Moritz{Arndt{Universitat Greifswald
vorgelegt von: Sergey Stepanov
geboren am 17. November 1980
in Sankt{Petersburg (Russland)
Greifswald, 26. April 2010Dekan: Prof. Dr. Klaus Fesser
1. Gutachter: Prof. Dr. Jurgen Meichsner
2. Gutachter: Prof. Dr. Uwe Czarnetzki
Tag des Promotionskolloquiums: 09. Juli 2010Contents
Abbreviations iii
List of symbols v
General introduction 1
1 Fluorocarbon RF plasmas 5
1.1 Fluorocarbon plasmas and their applications . . . . . . . . . . . . . . 5
1.2 Capacitively coupled RF discharges . . . . . . . . . . . . . . . . . . . 7
1.3 Gas phase processes in uorocarbon plasmas . . . . . . . . . . . . . . 10
1.4 Reactive plasma{surface interaction . . . . . . . . . . . . . . . . . . . 15
1.5 Diagnostic methods for gas phase analysis in uorocarbon plasmas . . 17
1.6 Experimental techniques for uorocarbon thin lms characterization . 20
2 Basics on molecular spectroscopy 23
2.1 Structure of molecular spectra . . . . . . . . . . . . . . . . . . . . . . 23
2.1.1 Vibrational energy levels and transitions . . . . . . . . . . . . 24
2.1.2 Rotational energy levels and transitions . . . . . . . . . . . . . 27
2.1.3 Vibrational-rotational transitions . . . . . . . . . . . . . . . . 29
2.2 Basic principles of absorption spectroscopy . . . . . . . . . . . . . . . 29
2.2.1 Beer-Lambert law . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2.2 Absorption line prole . . . . . . . . . . . . . . . . . . . . . . 31
2.2.3 Linestrength . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3 Experimental set-up and data acquisition 37
3.1 Vacuum apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2 IR Tunable Diode Laser Absorption Spectroscopy (IR{TDLAS) system 40
3.2.1 Lead salt diode lasers . . . . . . . . . . . . . . . . . . . . . . . 40
3.2.2 Optical table, laser tuning and beam guidance . . . . . . . . . 44
3.3 Data acquisition and TDLWintel software . . . . . . . . . . . . . . . 49
3.3.1 "Stream-Mode" approach . . . . . . . . . . . . . . . . . . . . . 51
3.3.2 "Burst-Mode" approach . . . . . . . . . . . . . . . . . . . . . . 52
i4 Preliminary investigations on relevant spectroscopic data of the target
molecules 55
4.1 Spectroscopic data of CF radical . . . . . . . . . . . . . . . . . . . . . 55
4.2 Spectroscopic data of CF radical . . . . . . . . . . . . . . . . . . . . 602
4.3 Spectroscopic data of the stable reaction product C F . . . . . . . . 602 4
4.3.1 C F preparation by vacuum pyrolysis of polytetrauoroethylene 612 4
14.3.2 Calibration of the C F absorption structure at 1337.11 cm 642 4
5 Absolute number density and kinetics of the target species in pulsed
CF /H rf plasmas 694 2
5.1 Plasma process parameters selected for investigations . . . . . . . . . 69
5.2 Characterization of the pulsed discharge mode . . . . . . . . . . . . . 72
5.3 Broad band FTIR spectroscopy of stable gaseous reaction products . 74
5.4 Target species and general approach to analysis of their reaction kinetics 78
5.5 Absolute number density traces of CF radical . . . . . . . . . . . . . 802
5.5.1 CF behavior during the "plasma-o " phase . . . . . . . . . . 802
5.5.2 CF radical in the "plasma-on" phase . . . . . . . . . . . . . . 832
5.6 Absolute number density traces of the reaction product C F . . . . . 862 4
5.6.1 C F behavior during the "plasma-on" phase . . . . . . . . . . 882 4
5.6.2 C F production in the "plasma-o " phase, correlations with2 4
CF radical . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
5.7 Absolute number density traces of CF radical . . . . . . . . . . . . . 96
5.7.1 CF radical kinetics in the "plasma-o " phase . . . . . . . . . . 100
5.7.1.1 Inuence of the electrode surface temperature . . . . 105
5.7.2 CF radical kinetics during the "plasma-on" phase . . . . . . . 108
6 Summary and outlook 117
A Appendix 123
A.1 First order ordinary di erential equations . . . . . . . . . . . . . . . . 123
A.1.1 General Riccati equation . . . . . . . . . . . . . . . . . . . . . 123
A.1.2 Linear equation . . . . . . . . . . . . . . . . . . . . . . . . . . 124
A.2 Calculation of the rate coe cient from the cross{section . . . . . . . 124
A.3 List of equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
Bibliography 127
iiAbbreviations
a-C:F amorphous uorocarbon (thin lm or layer)
AS Absorption Spectroscopy
AFM Atomic Force Microscopy
ATR{FTIR Attenuated Total Re ection Fourier Transform InfraRed
CCP Capacitively Coupled Plasma
c.w. continuous wave (plasma operation)
D/A Digital{to{Analog (convertor)
DC Direct Current
ECR Electron Cyclotron Resonance
EEDF Electron Energy Distribution Function
FTIR Fourier Transform InfraRed (spectroscopy)
HWHM Half{Width at Half{Maximum
IC Integrated Circuit
ICP Inductively Coupled Plasma
IR InfraRed
IR{TDLAS InfraRed Tunable Diode Laser Absorption Spectroscopy
IR{QCLAS InfraRed Quantum Cascade Laser Absorption Spectroscopy
LIF Laser Induced Fluorescence (spectroscopy)
MCT Mercury Cadmium Telluride (HgCdTe)
MFC Mass Flow Controller
MS Mass Spectrometry
MWI MicroWave Interferometry
NIST National Institute of Standards and Technology
OES Optical Emission Spectroscopy
PE PolyEthylene
PECVD Plasma Enhanced Chemical Vapor Deposition
TMPTFE PolyTetraFluoroEthylene (Te on )
QCM Quartz Crystal Microbalance
RIE Reactive Ion Etching
RF Radio Frequency
SNR Signal{to{Noise Ratio
TDLAS Tunable Diode Laser Absorption Spectroscopy
TTL Transistor{Transistor Logic
iiiAbbreviations
UV UltraViolet
VUV Vacuum UltraViolet
XPS X{ray Photoelectron Spectroscopy
ivList of symbols
A Honl-London factor
A powered (grounded) electrode area1;2

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