INDIAN INSTITUTE OF
NEW
TECHNOLOGY
DELHI-110016, INDIA
DELHI
八壇
ICROCRYSTALLINE DIA
八4OND THIN FILMS BY HOT FILAMENT CHEMICAL VAPOUR
DEPOSITION PROCESS
NITA DILAWAR
Thesis submitted
in fu/ti/ment of the requirements for the award of
DOCTOR OF PHILOSOPHY PHYSICS
Department of Physics
FEBRUARY, 1997
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I am satisfled that the Thesis entitled 明石とrocグ辞d襲ne Dたmond Thin月Ims By Hot-員Lainent Chemical Vapour Depo議加n Process ", presented by N如 Dたwar is worthy of consideration for the award of degree of加dor of Ph泌op/ty and is a rα刃rd of the original bonafide re欧誠迂ch work carried out by her under my gui山mce and supervision and that the results con面ned in it have not玩比n sub面廿ed in part or fuft to any other university or institute for the award of any degree or diploma.
Date：フo！ュ1八つ
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‘Dr. V.D. Vankar 乃ぴ厨or of Physics and Elecク.onicルtate riais Thin Film Laboratory, Department of乃りsics Ir威αn Instit開re of Technolo訂，Delhi 入ヒw Delhi-h1O 01呪力,dia
Acknowledgements
I wish to e甲ress 四gル直t汝た to Prびssor V. D．た川加rfor 厨 mya加able guida.'記e, positive criticism and zり(iv'直on. Rむ con皿'v町 encourageni昭ル and concern during the execution ofthe present work would be rem如めered而'h grat加ル巳sfor all だmes to come・
i would a励 wish to ac幻lowたdge the he女ゆI disc以競ons 碗rh Pr啄ssor K. L.
Ch叩ra. I 碗功 to 話奴nkPrぴ'ssor L. K. Maihotra for niロking the req厨ite ffi心崩賀 readily available. I am grat加ltoDr. B. R．ルfeん奴for his help and suggestio薦． The heい rendered by all other facu如 m朗めeバ of 乃in Film Labor'万07)1 S aムo gral加l'y acknowledged.
乃αnお areα加due to Dr. Br'功mn Prakiおh for help in adhesion and wear studi賀・J would aムo like to take thむ叩アorn'.nりto話協nkPr吠ssor H. D. Bist, Dr. A.
Prad切nandMs. C万eta/i Royfor Ra.'nan i肥asurements. I am aムo gral加ltoMr. D. C.
Shanna, Dr. C万artar Singh and Mr. V. Khanna for assistanてe in SA日:f studies.
I would be failing in my dめびI do not express my sincere gratil汝た to Rahul んpil and Somna S. M姉可an for their unti万ng and readily available help during 伽es of need and under pressing circwぼtances. I am i luたbted to T. Rajagopalan, O. K.
Varghese, Seema Agarwal, Harish Barshilia, Pル匠sん話協P'而り，Qamar Ak切i, Rajneesh S)切rma,R. V.R.Mレil勿，G'叩alK.ル勿r and :町naikfor their help at vario町stages of this work. I am a加grat加i to Suj'質Chatu劫αry, M. K. Ja/fl, Veer Singh, Acharya, P.
D. Pauムon and T. D. Sen for providing a liveか如nαァhere for work.
Finally, I wish to con',りりi放たbted,肥ss to my parents and my brothers糾吸o have borne而thme the dりto 'iりtensions and切riles. I wish to ti奴nk themfor all thりhave gone through.
ル脅、刃ルー 入伯aI瓦kwar
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Table of contents
Page No.
CERTIFICATE
ACKNO 晒 IJEDGEMENTS LIST OF FIGURES
ABSTRACT
C 瓦 M1ER I 、 INTRODUCTION
LO Introduction
i.i The diamond problem
i.I.1 The phase diagram of diamond
i. i .2 High pressure-high temperature synthesis
i . I .3 いw pressure-low temperature growth of diamond i .2 Structure, properties and applications
1.2. 1 Structure of diamond, graphite and diamond like開吐刃n i.2.2 Prope血es of diamond
1.2.3 Technological applications of diamond thin flims 1.3 The techniques for synthesis of diamond thin flims
i . 3 . 1 Hot-fllament chemical vapour deposition
1.3.2 Microwave plasma enhanced chemical vapour deposition 1.3.3 DC&RF plasma chemic司 v毎刃ur deposition
1.3.4 Combustion flame synthesis
i .4 Current status of low pressure synthesis of diamond i .5 The mechanism of diamond growth by HFCVD process i .6 Characterization of diamond thin films
i .7 High energy ion irradiation of diamond thin flims i.8 Aim of the present work
i .9 Pian of Thesis
CHAPIER II EXPERIMENTAL ASPECTS
2.0 Introduction
2. 1 Hot-fliament chemical vapour deposition system 2.1.i The system geom
山
y2.1.2 System conffiguration
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33 33 34 34 34 34 35 35 38 38 38 39 39 42 43 43 43 45 45 45 45 48 49 49 2.2 Substrate pr叩aration
2.2.1 Sub割m訓bpolishi面g 2.2.2 Substrate cleaning 2.3 System operation
2.3.1 C山もurization of the filament 2.3.2 氏釣sition start up興心司ure
2.4 Diamond window fabrication for叩tical studies 2.5 丘radiation at MビVenei著ies
2.6 Charac紀山副加n 奴hniques 2.6.1 Structuralch加口C肥n妾ttion
2.6.1.i Scanning electron 面croscopy 2.6.1.2 Glancing angle x-ray diff血ction 2. 6. 1 .3 Micro-Raman spectroscopy 2.6.2 T皿ckness measurem叫t
2.6.3 Tribological c比山にtenロtion
2.6.3. 1 Scratch adhesion tester 2.6.3.2 Wear studies
2.6.4 Opti国charac肥ガzation
2.6.4.1 恥urier transform mnfra-red spectroscopy 2.6.5 Elemental analysis
2.6.5.1 Elastic recoil detection analysis (ERDA) 2.6.5.2 Energy dispersive x-rays analysis (EDAX) 2.6.6 且叩trical ch紅敵な盛zation
2.6.6. 1 Resistivity measurements
CHAFFER lu DIAMOND THIN FILMS BY HFCVD 3.0 Introduction
3.1 _Experimen叫details 3 . 2 Results and discussion
3.2.1 Nucleation 如idies
3.2.2 Effect of 喚刃sition pむ meters 3.2.2.1 . E臣ct of gas ratio
3.2.2.2 E価叩t of working pressure 3.2.2.3 E拓ect of substrate temperature 3.3 mnfra-red trans面ssion studies
3.4 Conclusions
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CHAPTER IV STUDY OF HYDROGEN IN DIAMOND THIN FILMS
4.0 Introduction
4.0. 1 Elastic recoil detection analysis 4. 1 Hydrogen analysis by ERDA
4.1.i Determination of hydrogen concentration with ERDA 4. 1 .2 Determination of ratio of C and H atoms
4.2 Experimental details
4.3 Hydrogen concentration in polycrystalline diamond thin flims 4.3.1 E価叩t of gas ratio
4.3.2 E任叩t of working pressure 4.3.3 Effect of substrate temperature
4.4 Quantitative measurement of carbon and hydrogen 4.5 Study of hydrogen concentration in DLC flims 4.6 Conclusions
CHAVrER v HIGH ENERGY ION IRRADIATION STUDIES
5.0 Introduction 126
5. 1 Experimental details 128
5.2 Results and discussion 131
5.2.1 Effect of high energy ions on diamond thin flims 131 5.2.1.1 Irradiation with 50 MeV Si7+ ions 131 5.2.1.2 丘radiation with 100 MeV I7+ ions 140
5.2.1.3 Discussion 147
5.2.2 E価ct of 50 MeV Si4+ ions on diamond/DLC thin films 巧3
5.3 Conclusions 162
CHAFfER VI DIAMOND THIN FILMS ON TUNGSTEN CARBIDE AND METALLIC SUBSTRATES
6. 1 Diamond coatings on tungsten carbide 6.1.i Experimental de面Is
6. 1 .2 Results and discussion
6.2 Diamond thin coatings on metallic substrates 6.2.1 Experimental details
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6.2.2 Results 加d di記ussion 182
6.2.2. 1 Diamond thin coatings on ref即加ry metal substrates 182 6.2.2.3 D畑mond thinα加itings on nan-re丘actory metals i 86
6.3 Large area HFCVD system 189
6.3. 1 OEe system geometry 190
6.4 Conclusions 193
CHAFfER Vn CONCLUSIONS AND SCOPE OF FURTHER WORK
7.1 Conclusions
7.2 Scope of further work
