Chapter 1

Introduction

1.1 Definition of Plasma

Plasma is popularly known as the fourth state o f matter prevailing more than

99% o f our universe; we, residing in earth belong to the tiny rest. American chemist

Irving Langmuir first introduced the word “plasma” to electrical discharges during

1926-28 [1,2]. Plasma has drawn attention to scientists, engineers, biotechnologists

and industrialists since it had been popular for basic study, application science, a

source o f generation o f energy for future and considered as a frontier between

physicists and technologists. The tremendous potential delivered in this novel field

has lead to new ways o f producing plasma, fascinating materials, fusion energy,

numerous patents and various industries.

Matter in the near vicinity o f earth surface exists in the form o f three states -

solids, liquids and gases. Interestingly, given enough energy to the gaseous state

above the ionization potential o f the atom, there is a transformation o f short-range

forces existing in the gas to the long-range columbic forces. The result is that the

new state behaves differently and a collection o f charged particles are produced in

the background o f the neutral gaseous environment. Due to transitions between

different states o f the atoms, molecules, their excited and ionized states, photons are

emitted and a glow is observed. This “Collection o f electrons, ions o f atoms and

molecules in the vicinity o f neutrals and photons governed by columbic forces can

be regarded as “plasma”. The charged and neutral particles form a quasi neutral gas

1
 Chapter 1: Introduction

(n,- (electron density) = ^ (ion density) = n (neutral density)} dense enough so that

the debey length (XD) is much smaller than the dimension o f the system (L), have

enough charged particles {No = n (4/3) I~1Xd3 » 1 ) [3, 4] in the sheath region and

product o f frequency o f plasma oscillation (co) and mean time between collision (x)

should be high (cox>l), so that the motion o f charged particles are governed by

electromagnetic force rather than ordinary hydrodynamic force.

1.2 Plasma in Nature and Laboratory

Naturally plasma occurs in ionosphere between 90-400 Km above the surface of

the earth with a variation o f electron density o f 10n to 6*10u per m3 between 100-

300 Km. When the magnetic field o f earth interacts with charged particles coming

along solar wind beautiful pattern o f plasma known as aurora is produced. In

interstellar space, stars, nebulae and moving comets - plasma exists in abundance.

In laboratory, plasma has been produced by many techniques. A cathodic glow

discharge, plasma by filamentary discharge, inductively coupled plasma, high

frequency microwave discharge, a cathodic arc, dielectric barrier discharge, post

magneton discharge, fusion plasmas and laser produced plasma are the most

commonly used plasma for basic studies and applications.

1.3 Types of Plasmas

Plasmas are frequently subdivided into low (LTP) and high temperature

plasmas (HTP). A further subdivision relates to thermal and non-thermal

plasmas. Low temperature plasmas (LTP) are divided into thermal LTP and

non-thermal LTP. Electron and ion temperature in case o f thermal LTP is Te »

Ti « T < 2 x 104 K whereas T, * T * 300 k and Ti « Te < 105 K in case of

?
 Chapter 1: Introduction

non-thermal LTP. Arc plasma at normal pressure is an example o f thermal

LTP while low-pressure glow discharge is an example o f non-thermal LTP.

High temperature plasmas (HTP) have T; « Te > 107K. Fusion plasma belongs

to high temperature plasma [5].

As a classification o f pressure, low-pressure plasmas belong to the class o f non-

equlibrium plasmas while high-pressure plasmas are called equilibrium plasmas.

Cathodic glow discharge, filamentary glow discharges are some o f the non-

equlibrium plasmas where plasma temperature deviates from gas, ion and molecular

temperatures. A cathodic glow discharge at 1-10 torr pressure has 0.5-2 eV electron

energy, 10s- 1011 cm'3 electron density and lO^-lO'5 o f degree o f ionization [6].

While in high-pressure plasma like in a cathodic arc - electron, ion, gas and

molecular temperatures come closer so that a Local Thermodynamic Equilibrium

(LTE) can be approximated. In low-pressure plasma, deviation from LTE can be

seen and corona equilibrium relation can often applied.

A very important parameter for all non-equilibrium plasma is the reduced field

E/n; i.e., the electric field (E) divided by neutral gas density (n). In discharge

physics, this parameter has its own unit, viz. Townsend (Td). The reduced field

determine whether a plasma is equilibrium or not, only at low E/n values, electron

energy comes closer to kinetic energy o f heavy particles and equilibrium conditions

can exist. Non-equilibrium plasma is subdivided into following five discharges:

1) ,Glow discharge

2) Corona discharge

3) Silent discharge

4) RF discharge
'4 Chapter 1: Introduction

5) Microwave discharge

1.4 Plasma Diagnostics

Diagnostics applied to plasma determine the plasma parameters involved in a

particular experiment. Langmuir probe measurement is usefol in determining plasma

temperature and density in a cold plasma. Optical diagnostics like optical emission

spectroscopy (OES), laser induced fluorescence (LIF), Atomic mass spectroscopy

(AMS), Fourier transformed infrared spectroscopy (FTIR) are some good

spectroscopic techniques use&l in plasma diagnostics. Spectroscopic diagnostics

have the advantages that information can be collected from a plasma volume without

disturbing the plasma and depending upon spectroscopic data and resolution o f the

instrument various types o f parameters - atomic, molecular, ionic temperatures;

rates o f reactions [7], distribution functions etc can be estimated.

1.5 Optical Emission Spectroscopy (OES)

The optical diagnostic widely known as OES has been widely utilized to

glow discharge for its simplicity for identifying the plasma species and measuring

the emission remotely from the boundary o f plasma. Proper calibration of

wavelength by standard sources is needed to identify the plasma radiators. He-Ne

laser, Na lamp are commonly used for wavelength calibration while tungsten ribbon

lamp and carbon arc are used for intensity calibration. Tungsten ribbon lamp is

mostly used in visible region as a secondary intensity standard. On the other hand, in

near ultra violet and at shorter wavelength tungsten ribbon lamp emits weakly and

therefore is not suitable. Carbon arc, a high intensity source instead can be used in

these shorter wavelength side. In most cases, relative emissions are considered to

4
 Chapter 1: Introduction

avoid the complicacy o f performing absolute intensity calibration. In determining

absolute densities o f radiators the use o f these lamps is fairly a necessity.

Radiation emerged from plasma are generally collected at the output o f the

plasma system and the output has the effect o f filtered the radiator wavelengths. In

shorter wavelength side, best fused silica goes below 175 nm while ordinary fused

silica cuts off at 210 nm. Synthetic crystal quartz range goes down to 145 nm; vycor

glass cuts off at 240 nm, pyrex at 320 nm, crown glass at 350 nm and flint glass at

380 nm. In higher wavelength side, glasses transmit up to 2.5 micron, quartz up to 4

micron and sapphire to 5 micron. In uv-visible range fused silica and quartz are quite

useful as a wavelength transmitting media [8]. These materials are commonly

utilized in making lenses, windows and optical fibres, which are common media in

optical research and communication application.

Selection o f wavelength at the output o f a plasma column transmitting

through a suitable media can be done by a set o f slits, lenses and grating. A photo

multiplier tube or a multichannel plate at the output slit is able to measure the

radiation intensity. Intensities and wavelengths are the basic spectroscopic

parameters that are obtained from the experiment, the rest o f the derived parameters

are calculated from these two values, knowledge o f plasma density and temperature;

and availability o f spectroscopic data. Determination o f electron density and

temperature by conventional diagnostics and comparison as well as utilization o f

those parameters in spectroscopic calculation is often applied.

1.6 Atomic and Molecular Spectroscopy

By Spectroscopy we generally mean experimental charting o f the

energy level structure o f physical systems. The transition processes, spontaneous or

 Chapter 1: Introduction

induced; between different energy states are studied in spectroscopy as an analysis

of various types of radiation due to these transitions.

M olecular vibrations and fine structure transitions emit wavelength in

IR region while outer electron transition em it wavelength in visible and UV

range. The units for IR region are pm and cm '1 while for U V visible they are

nm and A, sometimes eV is also used, and the choice depends upon energy

region and traditional factors. The approximate relations between the various

units are described in [9].

hi weakly ionized plasma, broadening due to uncharged particles may be

important where interaction of neutral atoms at large distances has the form, V(R) x

R"6, and the typical value of width of a line y ~ 10'8 n [10].

1.7 Applications of Glow Discharge Plasmas

Applications o f glow discharge plasma (GDP) from technological and industrial

point of view are tremendous. Starting from surface modification technologies to

semiconductor fabrication, the boundaries of applications of GDP go beyond.

Production of new modified surfaces by nitriding, carburizing, nitrocurburizing, ion-

implantation; diamond like carbon (DLC) by plasma assisted chemical vapor

deposition (PACVD), nano materials like carbon nano tube by PACVD or by

thermal plasma/dense plasma focus, alternative source of fuel (Fuel Cell); designed

glasses by PACVD, technology for cutting hard materials by plasma arc; design for

semiconductor fabrication by plasma etching and large view monitor system known

as plasma display panel (PDP) show the immense number o f applications o f GDP
 Chapter 1: Introduction

(and also o f plasma in general). Classification o f various plasma technologies for

surface modification follows as:

1) Surface modification technologies

a) Plasma nitriding (PN)

b) Plasma carburizing (PC)

c) Plasma nitro carburizing (PNC)

d) Plasma boriding (PB)

2) Coating technologies

a) Plasma vapor deposition (PVD)

b) Plasma assisted chemical vapor deposition (PACVD)

c) Plasma spraying (PS)

3) Nanotechnology

a) Thermal plasma (TP)

b) Atmospheric pressure glow discharge (APGD)

4) Semiconductor Fabrication

a) Plasma etching (PE)

b) Sputtering

Due to tremendous growth o f processing plasma in material science, the basic

science and testing procedure has to be studied in detail lbr a better reliability o f

output surface.

1.8 Plasma Nitriding (PN)

Plasma assisted nitriding or simply plasma nitriding (PN) is a new type of

surface modification technique. It was first discovered in Germany in 30’s as a

replacement and modem technique over conventional gas nitriding process. Since

7
 Chapter 1: Introduction

then, many research groups and industries have studied this process in detail as a

basic science and industrial application. It is basically a surface modification

technique [11] where in abnormal glow [12, 13] o f glow discharge plasma, nitrogen

atom is embedded with a metal atom like iron and chromium present over a material

surface within micrometer range of the treated surface, to form metal nitrides and a

modified surface in terms o f better hardness, corrosion resistance and fatigue

strength is created. This special kind o f plasma for surface modification o f a material

can be termed as glow discharge plasma nitriding (GDPN) or shortly “nitriding

plasma”.

A brief summary o f Kolbel’s hypothesis [14] is that in nitriding mechanism,

sputtered iron reacts with atomic nitrogen in the gas phase to produce the

thermodynamically unstable iron nitride FeN. After condensation on a surface, FeN

releases atomic nitrogen, which may partially diffuse into the lattice yielding

subnitrides [13] or recombine to molecular nitrogen. This hypothesis is specially

tailored to a d.e glow discharge mechanism which is not compatible with ion-free

nitriding techniques, e.g., thermal ammonia gas nitriding.

Hudis [15] experiments showed that direct collisions o f ions with surface are

necessary to obtain hardening. Atomic nitrogen generated from a r f glow discharge

did not a nitride a plasma floated probe. A negative potential was necessary to

produce nitrides, the effect being proportional to the d.c current o f the biasing

potential, concluding in his statement that positive ions are responsible for the

plasma nitriding process. On the contrary, Tibbets [16] experiments have shown that

nitriding o f steel to occur even when positive ions have been repelled from the steel

8
 Chapter 1: Introduction

surface by a positively biased grid, concluding that nitriding takes pace by neutrals,

probably, by atomic nitrogen.

In general, the positive nitrogen ions, which are produced inside the glow

discharge, are attracted towards the negatively connected work pieces. They hit upon

the surfaces are thus occluded, and goes up to the necessary diffusion temperature.

This means an ionitriding furnace is purely a container with the purpose o f holding

an artificial vacuum inside and material treated serving as the anode for the glow

discharge. It does not have any classical heating device; a picture of plasma nitriding

of automotive tool is shown in Fig. 1.1. The voltage near the surface, which is called

cathode fall, is high and for Fe-N2 system it is 215 V [17],

Fig. 1.1 Plasma Nitriding of automotive tool, courtesy: Plasma Technik

Grim GmbH Postfach 210642 57030 Siegen Deutschland / Germany.

9
 Chapter 1: Introduction

During the plasma nitriding process, at the material surface the following

happens:

• Sputtering, cleaning and activation of the surface

• Heating of the work piece by absorption of kinetic energy of ions

• Reactions of highly active ions with elements in the work material

• Diffusion of elements - which are to be found in gas- into the work piece

Depending on the material and the results required, the treating temperature

and time are chosen in advance. Common advantages of the nitriding process by

using plasma are the following:

• No environmental and safety problems, as neither dangerous nitriding materials

are used nor produced

• Minimal requirement of gas, as, by ionizing, the gas used may be exploited

effectively

• The structure of the nitride layer may be controlled

• Surface parts which may not be treated, can be protected by covering

• Steels containing chrome may be nitrided without previous depassivation

• If required the temperature of work pieces may be kept very low; thus it is

possible to treat cold work steel

10
 Chapter 1: Introduction

DC plasma nitriding has many particular advantages over traditional salt bath

and gas nitriding in terms o f the reduced energy and gas consumption as well as the

environmental benefits. Notwithstanding these benefits, there are a number of

limitations in the DC plasma nitriding process that relate primarily to the use o f the

work piece as an electrode in generating the plasma. Although efficient for heating

and for the treatment o f relatively simple shapes, difficulties arise when either large

loads or loads containing complex geometrical parts require treatment. Difficulties

in maintaining uniform chamber temperatures is one problem, as well as, damage

caused to work pieces due to arcing, which is inherent in the production o f a plasma

of this type. Furthermore, the uniformity o f treatment at edges is subject to some

concern also.

In short, the principal advantages o f glow discharge nitriding over the

conventional gas based techniques are: the reduced process duration, the elimination

o f ammonia which is substituted by a mixture o f hydrogen and nitrogen, or nitrogen

alone, the modifying o f the phase composition o f the nitrided layers produced, the

ability to treat parts. Moreover, the layers produced by glow discharge nitriding are

more resistant to wear and fatigue and show better plasticity than the nitrided layers

produced by the conventional gas techniques [18].

1.8.1 Background of Plasma Nitriding

Techniques for the hardening o f steel surfaces by nitriding have been

developed first by Fry [19, 20] and later by many others. The plasma nitriding

process was developed in Germany back in 1932. Because o f the advanced and

sophisticated nature o f the process, its industrial application is still very young.

Systems have been on the market since 1973. There are 37 production units working

11
 Chapter 1: Introduction

in west Germany, 10 in Japan, 6 in East Germany, 5 in Switzerland, 2 in Poland, 2 in

Spain, 1 in Romania, 1 in Australia and 1 from Klockner Ionon GmbH in west

Germany has either supplied or controls the 65 units. Total nitriding capacity o f

these units is about 80000 tons per year. Production experience indicates that

properties like wear resistance, gliding properties; ductility, hardness and fatigue

strength surpass those o f conventionally nitrided pieces.

1.8.2 Nitrided Layer Structure

T he w hite layer w ith m edium to high nitrogen and low carbon

concentration also know n as com pounded layer has thickness o f th e order

o f tens o f p m (the epsilon phase, e), w h ile w ith low nitrogen and zero

carbon potential produces another w hite layer consisting o f a single

nitride phase o f the from Fe 4N (gam m a prim e phase, y ’). Its thickness is

usually below the once o f epsilon phase, even after long treatm ent it does

n o t exceeds ten o f pm . T his is a v ery special w h ite layer w ith very

specific ductile properties and produced b y p lasm a nitriding only in an

industrial scale. W ith use o f very low intruding potential form ation o f

w hite layer can be avoided. T he diffusion layer below th e com pound layer

has ductility steadily decreasing w ith increasing hardness and increasing

thickness o f the layer. T his th ird k in d o f layer is u sed in to o l nitriding

because it offers m axim um ductility [21].

12
 Chapter 1: Introduction

1 .9 P la n o f th e T h e s is

1.9.1 Literature Study

Contradictory opinions and hypothesis have caused uncertainties about the

elementary chemical and physical processes involved in plasma nitriding.

Optimizations have been carried out based on empirical estimation only, since

insufficient knowledge of the elementary processes are available. Recent interest has

been centered on optical emission spectroscopy (OES) as a tool for diagnostics and

controlling the constituents in the coating discharge and to thereby obtain a better

insight into the discharge phenomena and elementary processes responsible for

nitrogen incorporation into the substrate [22]. Plasma nitriding has already reached

an industrial stage, however, it is necessary to fully optimize the process, since

explanations given for the species governing the surface nitriding o f metals and

microscopic processes involved are full o f contradictions.

Existing work in literatures have shown progress in emission spectroscopy in

N 2, N 2/H 2 or in W A r plasmas and nitriding in those various gas mixtures with

characterization o f different materials have been reported widely. Pulsed plasma

used for nitriding is useful for atomic spectrometry; however, an improved

design o f the source is necessary [23]. Production o f plasma for nitriding by

special kind o f sources is thus indispensable for a better surface and quality

species; production o f such plasma with variable frequency o f source in kHz

region has been depicted in Chapter 2 where the setup o f plasma nitriding unit

is described. Considerable effort has been made in finding the influence of

hydrogen in DC and DC pulsed N 2/H2 glow discharges [24] by OES and Laser

induced fluorescence (LIF) while rotational and vibrational temperature (Tv) o f N 2

13 A C c . K n > ■i ' T
 Chapter 1: Introduction

molecule by OES has also been studied [25]. Rotational temperature (Tr) found by

OES in pulsed corona discharge reported to be around 500 K [26] while Tr as a

function of time has also been studied [27]. Effect of hydrogen gas on nitriding by

OES, determination of Tv and comparison of Tvwith Te are experimented in Chapter

3, 5. Pulsed discharges are of interest because they allow one to avoid arc formation

in the work pieces, to limit the surface sputtering and to pursue the treatment in the

post-discharge regime by long-lived species. Active species in N2 discharges are

metastable molecules like N2 (A), N 2 (X,v) vibrational states, N atoms, 1ST atomic

ions. Nitriding of steel is greatly influenced by the presence o f hydrogen because of

the strongly oxide reducing effect of the hydrogen atoms [28]. OES study has

indicated that the dominant ionic species arriving at the cathode o f a pure nitrogen

dc discharge is N*, even though N2+ is the main ion populating the plasma region

[29]. The active species N, N 2+, N2 (B3pig) and N 2 (C3piu) have been extensively

studied by emission spectroscopy, while the vibrationaly excited molecules in the

electronic ground state N 2 (x!pig+, v) and H2 (x1pig+, v) are also important in N 2-H2

plasma nitriding [30].

In N2/CH4 mixture, the spectra reveal the presence of CN band in addition to

N 2 and N 2+ [31], moreover, agreement between measured and calculated

concentration of N 2 states found to be excellent. The electron collision processes of

nitrogen molecule is interesting in order to obtain various N, N2 and N2+ states, the

collisional-radiative processes involved in these processes have been reported [32]

while N2 vibrational temperature has been calculated by theory [30] in N2/H2 gas

mixtures as a function of concentration of H2. Pulsed plasma nitriding provides

special advantages that nitriding properties can be obtained at low heat-treating

14
 Chapter 1: Introduction

temperature [33] whereas nitriding in radio frequency (rf) discharge produces much-

increased rate o f nitriding [34]. Successful nitriding of austenitic stainless steel has

been achieved using an inductively coupled r f nitrogen plasma with exceptionally

high hardness [35]. Thin iron oxide layers, Fe304, inhibit the nitriding reaction, to

avoid this, Hh gas has been introduced in N2 plasma and thickness o f Fe4N layer

with respect to N/N2 dissociation rate has been reported [36] in Ar/N2,gas mixtures,

while nitrogen molecular dissociation with emphasis on N2+-N2° dissociative charge

exchange has been studied [29]. Molecular dissociation in a microwave discharge

operating in N2-H2 mixture has been studied and reported [37]. Effect o f hydrogen

gas on hardness and nitride formation by characterizing austenitic stainless steel

materials is a subject o f result by experimentation in Chapter 3. Discharge behaviour

is found to be dependent on applied voltage, gas pressure, pulse duration and pulsing

frequency in a pulsed high-voltage glow discharge [38]. The influence ,of excitation

frequency in glow discharge is reported [39, 40, 41] and found to be a factor, which

controls nitriding [18]; the driving rf frequency has been found to affect significantly

on molecular fragmentation [42]. The most luminous discharge area in the nitriding

plasma is the negative glow where species like N2, N2+, NH and Fe are found [22].

The correlation between nitriding and spectroscopy has been studied [43]. The

spectroscopic detection o f emitting species generally used a grating; a Czemy-

Tumer mount [44, 26] is often applied for the light arrangement. Excitation and

ionization o f species, v-v transitions along with vibrational energy distribution

function (vedf) [45] are becoming important issues in plasma nitriding. Other

distribution functions like electron energy distribution function (eedf) for vibratonal

temperatures 1500 K, 3000 K and 6000 K considering collision o f electrons with

15
 Chapter 1: Introduction

vibrationally excited molecules has been reported [46] and determination rate

constants in this kind of study is useful [47]. Time varying N2, N2+ intensities have

been studied [28], nitrogen second positive system was observed [48], N atom

density is correlated to surface [49], active species density and growth of iron nitride

layer are correlated [50]; some of these variations and correlations are discussed in

Chapter 3. Determination of density of species by mass spectroscopy is found to be

feasible [51], modification of nitrogen spectrum as hydrogen is added is notable [52]

and their growth as a function of pressure, position and time are vital [53]. Optical

emission near biased electrode showed pre-sheath/sheath region rapidly shrinking

with increasing pressure [54], N2+ ground and excited state densities as a function of

position has been reported [55] and it is a matter of experimentation in Chapter 4 in

terms of OES intensities. The OES diagnostic is also successfully applied to other

application like Si and Si02 etching [56]. In Ar/N2 plasma [57], the N2 states seen

in N2/H2 plasma [58] are also observed and studied in terms of depositing TiN [59].

Pure Ti and Ti alloy nitriding and carburizing at 900 °C has been reported [60]

while carburizing at high temperature of 1040 °C has also been studied [61]. T f

signal has been detected by OES at 323.6 nm in PACVD treatment in depositing

TiN [62], which has also been produced by PN process [63]. AISI 304 steel nitrided

and studied with respect to duty cycle, gas mixture and time along with CrN

formation [64], In duplex treatment (plasma nitriding after chromizing), CrN found

to be mixed with iron nitride [65], while y-iron nitride is dominant in laser

nitriding [66] that is also formed by PN process. AIN type of nitrides are

superior in terms of obtaining excellent hard surface [67, 68]. In nitriding with any

mixture, nitrogen dissociation [69] is crucial, either it is plasma nitriding, duplex

16
 Chapter 1: Introduction

treatment, high voltage glow discharge plasma implantation [70] or plasma

based ion implantation [71, 72, 73], Electron density which is normally found

by Langmuir probe can also be determined by optical emission actinometry

and has been studied as a function o f rf power [74], Te o f ICP plasmas at

different axial distances has also been determined by this method [75], Plasma

parameters, which indirectly controls nitriding, are thus o f serious concern

either in positive column or in negative glow o f discharge. Consequently,

electron temperature and density determination by theory [76] as well as in

experiment are important [77, 78] while electron density found from line

intensity measurement [79] provide a comparison o f OES with conventional

probe results. Complex radicals (like NH) are thought to control nitriding and

reactive constituents like NHo-4 , FeNH 2-3 in cathode surface glow area [20]

have been detected. Excitation frequency o f plasma source (of power supply),

which is a subject matter o f study in this thesis in Chapter 5, has been studied

theoretically [80] and experimentally (in nitriding) [18]. OES has been found

to be dependent upon r f power and hence plasma power driven by excitation

(or source) frequency is a major parameter o f variation, atomic N emission lines

(745 nm, 869 nm) are found to vary significantly with this parameter [81].

Extension o f current plasma nitriding experiment to Active Screen Plasma

Nitriding (ASPN) technique, study by other spectroscopic diagnostic like

mass spectroscopy, applying optical emission actinometry for plasma density

determination and probable formation o f super hard layer like AIN are

presented as some possible scopes o f the present work in Chapter 6.

17
 Chapter 1: Introduction

1.9.2 Synopsis of the Thesis

The main three objectives o f the synopsis o f the thesis were:

• To set up a plasma nitriding reactor consisting o f plasma production chamber,

pumping system, N2/H2 gas cylinders, mass flow controllers, capacitance

manometer, power supplies, Monochromator with PMT, optical bench, lenses,

fibre cable, Langmuir probe, probe biasing circuit etc.

• To identify the active species present in N2/H2 glow discharge plasma by optical

emission spectroscopy.

• To study the change in the spectral features and other plasma conditions with the

variation o f N2/H2 gas mixture as well as the discharge parameters like source

frequency, duty cycles etc., by using optical emission spectroscopy for

optimization o f plasma nitriding process.

However, nitriding o f steel samples and their characterization with emphasis on

austenitic type at different process parameters have been included in later course of

time.

1.9.3 Short Description of the Thesis

The wo,rk o f the thesis accordingly and primarily focuses on OES

diagnostics during glow discharge plasma nitriding and characterization o f plasma

treated steels in nitrogen hydrogen environment by hardness measurement and X-ray

diffraction (XRD). Langmuir probe diagnostics close to and at plasma nitriding

conditions is also incorporated for a comparison with OES. On one side, the process

o f plasma nitriding has immense industrial application for modification o f surface

properties; the spectroscopic measurement o f various excited and ionized states

gives a possible correlation o f the atomic and molecular parameters with nitriding

18
 Chapter 1: Introduction

properties. Nitriding o f locally found tools is also tried to harden the surface for a

direct implication and commercialization o f this plasma assisted process.

In this Chapter, general introduction and brief review o f plasma and plasma

nitriding process are described along with OES diagnostics. The experimental setup

is explained in Chapter 2 with necessary description o f the accessories o f plasma

chamber and diagnostics used. In Chapter 3 , OES during plasma nitriding in terms

o f various intensity measurements o f active species present in N2 and N2/H2 gas

mixtures and with respect to various process parameters is depicted.

Characterization o f nitrided samples by X R D and hardness test is also reported. An

initial effort for hardening o f some special materials used in agricultural and

domestic implements are demonstrated. In Chapter 4 , O ES o f N2/N2+ vibrational

bands and A r I lines observed in N 2, H 2/N2 and Ar/N 2 plasmas are portrayed with

relevancfe to LP results. Effect o f plasma power on N2, N2+ intensities, plasma

discharge characteristics, calculation o f vibrational temperatures at different source

frequency conditions are explained in Chapter 5. In Chapter 6, summary,

conclusions and scope o f the thesis are presented. Finally, a list o f important

parameters o f plasma, units, conversions, constants and formulas used throughout

the thesis; O ES o f argon plasma in filamentary discharge and detection o f some

primary elements in sun are described in appendices A-C.

19
 Chapter 1: Introduction

References
[1] Y. Eliezer and S. Eliezer, The Fourth State o f Matter: An Introduction to The

Physics of Plasma, IOP Publishing Ltd. (1989) p. 160.

[2] H. V. Boenig, Plasma Science and Technology, Cornell University Press (1982)

p. 13.

[3] F. F. Chen, Introduction to Plasma Physics and Controlled Fusion, Second

Edition, Plenum Press, Vol. 1: Plasma Physics, New York and London (1990) p. 3,

10, 11.

[4] K. Nishikawa and M. Wakatani, Plasma Physics Basic Theory with Fusion

Applications, Second Edition, Springer-Verlag, Berlin, Heidelberg (1994) p. 6.

[5] R. Hippier, S. Pfau, M. Schmidt, K. H. Schoenbach (Eds.), Low Temperature

Plasma Physics Fundamental Aspects and Applications, Wiley-VCH Verlag GmbH,

Berlin (Federal Republic o f Germany) (2001) p. 15,16.

[6] B. Eliasson and U. Kogelschatz, IEEE Trans. Plasma Sci. 19 (1991) p. 165.

[7] J. L. Franklin (Edited by), Ion-Molecule Reactions, Part I: Kinetics and

Dynamics, Benchmark Papers in Physical Chemistry and Chemical Physics, Vol. 3,

Dowden, Hutchinson & Ross, Inc. USA (1979) p. 63.

[8] H. R. Griem, Plasma Spectroscopy, McGraw-Hill Book Company, USA (1964)

p. 228.

[9] S. Svanberg, Atomic and Molecular Spectroscopy, Basic Aspects and

Practical Applications, Second Edition, Springer Verlag, Berlin, Heidelberg

(1992) p. 1,2,3.

20
 Chapter 1: Introduction

[10] I. I. Sobelman, L. A. Vainshtein and E. A. Yukov, Excitation o f Atoms and

Broadening o f Spectral Lines, Second Edition, Springer-Verlag, Berlin, Heidelberg

(1994) p. 289, 290.

[11] P. I. John (Edited by), Plasma Processing Update, Newsletter, Issue 40, FCIPT,

IPR (2002) p. 3.

[12] B. Chapman, Glow Discharge Processes: Sputtering and Plasma Etching, John

Wiley & Sons, New York (1980) p. 95.

[13] A. Grill, Cold Plasma in Materials Fabrication, IEEE Press, New York (1994)

p. 24-31.

[14] J. Kolbel, Die Nitridschichichtbildung bei der Glimmentladung,

Forschungsbericht des Landes NRW Nr. 1555, Westdeutscher Verlag, Koln/opladen

(1965).

[15] M. H udis, J. A ppl. Phys. 44 (1973) p. 1489.

[16] G. G. Tibbets, J. Appl. Phys. 45 (1974) p. 5072.

[17] P. Raizer, Gas Discharge Physics, Springer-Verlag, Berlin, Heidelberg (1991)

p. 182.

[18] T. Wierzchon, J. Rudnicki, M. Hering, R. Niedbala, Vacuum 48 (1997) p. 499.

[19] A. Fry, Stahl Eisen43 (1923) p. 1272.

[20] A. Szabo and H. Wilbelmi, Plasma Chem. Plasma Proc. 4 (1984) p. 89,

95, 97.

[21] B. Edenhofer, P roduction Ionitriding Source B ook on Ionitriding,

C om piled by Publication D evelopm ent A m erican Society for M etals

(1977) p. 181, 182.

21
 Chapter 1: Introduction

[22] B. Kulakowska-Pawlak and W. Zymicki, Thin Solid Films 230 (1993) p.

117.

[23] J. A. Del Val, S. Mar, M. A. Gigosos, I. De La Rosa, C. Perez, and V.

Gonzalez, Jpn. J. Appl. Phys. 37 (1998) p. 4177.

[24] ¥ . Scherentz and G. Henrion, Plasma Sources Sci. Technol. 9 (2000) p.

32.

[25] R. B leekrode and W . V . B entham , J. A ppl. Phys. 40 (1969) p. 5277,

5279.

[26] F. Tochikubo, T. H. Teich, Jpn. J. Appl. Phys. 39 (2000) p. 1343, 1348.

[27] K. Saito, T. Sakka and Y. H. Ogata, J. Appl. Phys. 94 (2003) p. 5533.

[28] B. J. Gomez, S. P. Bruhl, J. N. Feugeas and A. Ricard, J. Phys. D: Appl.

Phys. 32 (1999) p.1239.

[29] K. S. Fancey, Vacuum, 46 (7) p. 695, 696.

[30] J. Louriero and A, Ricard, J. Phys. D: Appl. Phys. 26 (1993) p. 168.

[31] C. D. Pintassilgo, G. C em ogora and J. Louriero, Plasma Sources Sci.

Technol. 10 (2001) p. 148.

[32] A. Garseadden and R. Nagpal, Plasma Sources Sci. Technol. 4 (1995) p.

270.

[33] H. Uwe, ASM International Heat Treating Conference, Equipment and

Processes, Chicago, Illinois, 18-24 April (1994).

[34] A. Szasz, D. J. Fabian, A. H endry & Z. Szaszne C sih, J. A ppl. Phys.

66 (1989) p. 5598.

[35] F. El-Hossary, F. Mohammed, A. Hendry, D. J. Fabian, Z. Szaszne-Csih, Surf.

Engg. 4 (1988) p. 154.

22
 Chapter 1: Introduction

[36] A. R icard, J. E. O seguera-Pena, L. Falk, H. M ichel and M . G antois,

IE E E Trans. P lasm a Sci. 18 (1990) p. 941, 943.

[37] E. Tatarova, F. M. Dias, B. Gordiets and C. M. Ferreira, Plasma Sources Sci.

Technol. 14 (2005) p. 20.

[38] X. B. T ian and P. K. Chu, J. Phys. D: Appl. Phys. 34 (2001) p. 354,

358.

[39] D. L. F lam m and V . M . D onnely, J. A ppl. Phys. 59 (1986) p. 1052.

[40] V. M. D onnely, D. L. F lam m and R. H. B ruce, J. A ppl. Phys. 58

(1985) p. 2135.

[41] F. Finger, U . K roll, V. V iret, A. Shah, W . B eyer, X. -M . T ang, J.

W eber, A. H ow ling and Ch. H ollenstein, J. A ppl. Phys. 71 (1992) p.

5665.

[42] S. M anolache, M . Sarfaty and F. D enes, Plasma Sources Sci. Technol.

9 (2000) p. 37,44.

[43] M. Capitelli and C. Gorse (Edited by), Plasma Technology Fundamentals

and Applications, Plenum Press, New York and London (1992) p. 137.

[44] R. H. Huddlestone and S. L. Leonard (Edited by), Plasma Diagnostic

Techniques, Vol II, Academic Press, New York, London (1965) p. 325.

[45] J. Levaton, J. Amorim, A. R. Souza and A. Ricard, J. Phys. D: Appl.

Phys. 35 (2002) p.689.

[46] H. Brunet, P. Vincent and J. R. Serra, J. Appl. Phys. 54 (1963) p. 4951,4953.

[47] G. Gallade, J. Deschamps, J. L. Godart and A. Ricard, J. Phys. D: Appl.

Phys. 24 (1991) p. 909.

23
 Chapter 1: Introduction

[48] S. P. Bruhl, M. W. Russell, B. J. Gomez, G. M. Grigioni, J. N. Feugeas

and Ricard, J. Phys. D: Appl. Phys. 30 (2002) p. 2917.

[49] A. Ricard, J. Phys. D: Appl. Phys. 30 (1997) p. 2261.

[50] H. Malvos, H. Michel and A. Ricard, J. Phys. D: Appl. Phys. 27 (1994) p.

1328.

[51] K. Ito, K. Hagiwara, H. Nakaura, H. Tanaka and K. Onda, Jpn. J. Appl.

Phys. 40 (2001) p. 1472.

[52] S. D. Popa, P. Chiru and L. Ciobotaru, J. Phys. D: Appl. Phys. 31 (1998) p.

L54.

[53] A. M. Diamy, L. Hochard, J. -C . Legrand and A. Ricard, Plasma Chem Plasma

Proc. 18 (1998) p. 451.

[54] E. C. Benck, A. Schwabedissen, A. Gates and J. R. Roberts, J. Vac. Sci.

TeehnoL A 16 (1998) p. 306.

[55] R. A. Gottscho, R. H. Burton, D. L. Flamm, V. M. Donnelly and G. P. Davis, J.

Appl. Phys. 55 (1984) p. 2708, 2709.

[56] R. d’Agostino, F. Cramarossa, S. De Benedictis and G. Ferraro, J. Appl.

Phys. 52 (1981) p. 1259.

[57] A. Ricard, H. Malvos, S. Bordeleau and J. Hubert, J. Phys. D: Appl.

Phys. 27 (1994) p. 504.

[58] L. Petitjean and A. Ricard, J. Phys. D: Appl. Phys. 17 (1884) p. 919.

[59] A. Ricard, P. Jacquot, H. Michel and M. Gantois, J. Phys. D: Appl. Phys.

18 (1885) p. 1701.

[60] P. Jacquot, M. Buvron and J. P. Souchard, Mat. Sci. Forum 102-104

(1992) p. 301.

24
 Chapter 1: Introduction

[61] W. L. Grube and J. G. Gay, Metallurgical Transactions A 9A (1978) p.

1421.

[62] K. S. Mogensen, S. S. Eskildsen, C. Mathiasen and J. Bottiger, Surf. Coat.

Technol. 102 (1998) p. 43.

[63] M. Konuma and O. Matsumoto, J. Less-common Metals 52 (1977) p. 145.

[64] E. Menthe and K. -T . Rie, Surf. Coat. Technol. 116-119 (1999) p. 199.

[65] D. Y. Chang, S. Y. Lee and S. G. Kang, Surf. Coat. Technol. 116-119

(1999) p. 394.

[66] P. Schaaf, M. Han, K. -P . Lieb and E. Carpene, Appl. Phys. Lett. 80

(2002) p. 1092.

[67] L. M. Sheppard, Ceramic Bulletin 69 (1990) p. 1801.

[68] G. Selvaduray and L. Sheet, Mat. Sci. Technol. 9 (1993) p. 463.

[69] G. Katz and R. Kosloff, J. Chem. Phys. 103 (1995) p. 9475.

[70] X. B. Tian, P. Peng and P. K. Chu, Phys. Lett. A 303 (2002) p. 67.

[71] W. Moller and S. Mukherjee, Curr. Sci. 83 (2002) p. 237.

[72] X. Tian and P. K. Chu, Rev. Sci. Instr. 71 (2000) p. 2839.

[73] M. A. Liberman, J. Appl. Phys. 66 (1989) p. 2926.

[74] N. C. M. Fuller, I. P. Herman and V. M. Donnely, J. Appl. Phys. 90

(2001) p.3182.

[75] V. M. Donnely, J. Phys. D: Appl. Phys. 37 (2004) p. R235.

[76] H. J. Kim, K. Matsuo, K. Muraoka and M. Akazaki, J. Phys. D: Appl.

Phys. 22 (1989) p. 1555.

[77] J. L. Jauberteau, I. Jauberteau and J. Aubreton, J. Phys. D: Appl. Phys. 37

(2004) p. 1242, 1243.

25
 Chapter 1: Introduction

[78] S. Ono and S. Teii, J. Phys. D: Appl. Phys. 16 (1983) p. 163.

[79] R. Hugon, M. Fabiy and G. Henrion, I Phys. D: Appl. Phys. 29 (1996) p.

761.

[80] R. H. Bruce, J. Appl. Phys. 52 (1981) p. 7064.

[81] A. V. Blant, O. H. Hughes, T. S. Cheng, S. V. Novikov and C. T. Foxon,

Plasma Sources Sci. Technol. 9 (200(3) p. 13,14.

26