Theoretical study of chemical vapor deposition of transition metal compounds [Elektronische Ressource] / vorgelegt von Magdalena Siódmiak

Informations

• Publié par: philipps-universitat_marburg
• Publié le: 01 janvier 2001
• Nombre de lectures: 16
• Langue: English
• Poids de l'ouvrage: 4 Mo

Extrait

Theoretical Study of Chemical Vapor Deposition of
Transition Metal Compounds
Dissertation
zur
Erlangung des Doktorgrades
der Naturwissenschaften
(Dr. rer. nat.)
dem
Fachbereich Chemie
der Philipps-Universität Marburg
vorgelegt von
Magdalena Siódmiak
aus Olsztyn/Polen
Marburg/Lahn 2001Vom Fachbereich Chemie der Philipps-Universität Marburg
als Dissertation angenommen am 24.01.2001
Erstgutachter Prof. Dr. G. Frenking
Zweitgutachter Prof. Dr. G. Boche
Tag der mündlichen Prüfung: 07.02.2001This work was completed at the group of Prof. Dr. Gernot Frenking whom I would like to
thank for providing an excellent working environment. To Anatoli Korkin I thank very much
for very interesting topic of my research and very fruitful cooperation. All my colleagues
from AK Frenking I would like to thank for help and time we spent together at the university,
and not only there ....Results of this thesis have been published in following papers:
1. Siodmiak, M; Frenking, G., and Korkin, A. J. Phys. Chem. A 2000, 104, 1186.
2. Siodmiak, M; Frenking, G., and Korkin, A Materials Science in Semiconductor
Processing 2000, 3, 65.
3. Siodmiak, M; Frenking, G., and Korkin, A J. Mol. Model. 2000, 6, 413.
4. Umanskii, S. Ya.; Novoselov, K. P.; Minushev, A. Kh.; Siodmiak, M; Frenking, G.,
and Korkin, A J. Comp. Chem. in press.Table of contents:
1. Introduction 1
2. Theoretical Background 5
2.1 Schrödinger equation ....................................................................................................5
2.2 Hartree-Fock approximation .........................................................................................6
2.3 Basis sets expansion and pseudopotentials ...................................................................8
2.4 Møller-Plesset perturbation theory ..............................................................................11
2.5 Coupled Clusters methods ..........................................................................................13
2.6 Density Functional Theory ..........................................................................................15
2.7 Periodic systems and Bloch’s theorem .......................................................................17
2.8 The k-points integration ..............................................................................................19
2.9 Chemical equilibrium ..................................................................................................21
2.10 Well-mixed reactor.....................................................................................................22
3. Initial Reactions in CVD of Ta O from TaCl and H O 252 5 5 2
3.1 Introduction .................................................................................................................25
3.2 Computational methods ..............................................................................................26
3.3 Results and discussion ................................................................................................26
3.3.1 Structure, bonding and vibrational frequencies of TaCl , TaOCl and TaO Cl ..275 3 2
3.3.2 Energies and structures of TaCl OH and TaCl (OH) .........................................324 3 2
3.3.3 Thermochemistry of gas phase reactions in the system TaCl /H O ....................365 2
3.3.4 Mechanism of hydrolysis of TaCl .......................................................................395
3.3.5 Mechanism of dehydration of TaCl (OH) ...........................................................413 2
3.3.6 Mechanism of HCl loss of TaCl OH ...................................................................444
3.4 Summary and conclusions ..........................................................................................474. Gas-phase reaction in CVD of TiN from TiCl and NH 494 3
4.1 Introduction .................................................................................................................49
4.2 Computational methods ..............................................................................................51
4.3 Complex formation and ammonolysis ........................................................................52
4.3.1 Four-coordinated titanium containing molecules ............................................52
4.3.2 Five-coordinated complexes ............................................................................55
4.3.3 Six-coordinated complexes ..............................................................................60
4.3.4 Thermochemistry and mechanism of ammonolysis .........................................63
4.3.5 Equilibrium gas mixture composition ..............................................................74
4.3.6 Elementary reaction rate constants ..................................................................77
4.4 Formation of imido complexes ...................................................................................86
4.4.1 Four-coordinated imido complexes .................................................................86
4.4.2 Five-coordinated imido complexes ..................................................................87
4.4.3 Six-coordinated imido complexes ....................................................................89
4.4.4 Thermochemistry and mechanism of imido species formation .......................91
4.5 Summary and conclusions ...........................................................................................97
5. Hydrogen adsorption at TiN (100) surface 99
5.1 Introduction ............. ..................................................................................................99
5.2 Computational methods ............................................................................................100
5.3 TiN properties ...........................................................................................................101
5.3.1 TiN bulk properties ........................................................................................101
5.3.2 TiN surface .....................................................................................................102
5.4 Hydrogen atom adsorption on TiN (100) surface .....................................................106
5.4.1 Molecular (cluster) model ..............................................................................106
5.4.2 Crystal (periodic slab) surface model ............................................................113
5.5 Summary and conclusions ........................................................................................1206. Conclusions 122
7. Zusammenfassung 125
8. References 131 1
1. Introduction
The formation of metal-containing thin-film materials is currently an area of immense
interest and research activity. These materials have found increasing application to a wide
variety of technological solutions within optoelectronic devices, electronic materials,
heterostructures, superconductive materials and device interconnects. Other applications of
metal-containing thin films use their high hardness and inertness. Thus one finds these
materials in chemically taxed aerospace components, high energy optical systems, high
temperature devices or as coating films in cutting tools.
Metal-containing thin films have been prepared traditionally by a number of techniques
which can be classified according to the film formation environment: electrolysis (e.g.
electrolytical anodisation, electroplating), vacuum (vacuum evaporation, ion beam deposition,
molecular beam epitaxy, ion implantation), plasma (sputtering deposition, ion plating), liquid
phase (liquid-phase epitaxy), solid state (solid-state epitaxy), and chemical vapor (substrate
chemical vapor conversion, chemical vapor deposition). Each of these techniques due to its
advantages and limitations is used in fabrication of metal-containing thin films for different
applications. In semiconductor devices and integrated circuits technology the best quality thin
films with very low defect density are provided by Chemical Vapor Deposition (CVD).
The technique of CVD is a relatively old chemical process, dating from the 1880s in the
1productions of carbon filaments for the incandescent lamp industry. Shortly after the initial
use of CVD for making carbon films, organometallic compounds found application in the
2formation of metal containing solid-state materials in vapor-phase processes.
Chemical vapor deposition, as its name implies, is a processes in whic