L37-G1+TG1-W-Plasma Enhanced

Chemical Vapour Deposition(PE-CVD)

BCl3 NH3 =+ BN +3HCl

NH3
BCl3
EXHAUST
V

BN Coating
t
STEEL SPECIMEN

HEATER: ~800 deg C

 PRINCIPLES OF CHEMICAL VAPOUR DEPOSITION
Chemical vapour deposition uses Surface Chemical Reaction to form a
coating
As with the case with other coating techniques, the surface needs to
be clean, polished to 20 nm rms or less and made free from surface
oxide layer.
Mostly steel/Si specimen are used as substrates.
Engineering components can also be coated with CVD
CVD technique uses two or more precursors in the form of gas or
vapour.
The precursors combine on surface normally kept above 500 degree C
to form a coating
Organo-metalic precursors are often used to reduce deposition
temperature

TUBULAR VACUUM
CHAMBER: 10-2 mbar
UNREACTED VAPOUR/
RELEASED GAS

Si3N4-COATING

HEATER
WHAT DOES THE PLASMA ENHANCEMENT DO?

PLASMA IMPOSES AN IONIZING MEDIUM

REACTIVE SPECIES BECOMES IONIZED

INTERACTION BETWEEN IONS IS MUCH

STRONGER AS IT IS ELECTROSTATIC

BOTH GAS PHASE AND SURFACE REACTIONS

OCCUR

DEPOSITION RATE IN TERMS OF

MICROMETERS /PER HOUR IS POSSIBLE

time
MOST IMPORTANT ASPECT OF PLASMA
DEPOSITION IS, BIASING CAN BE IMPOSED TO
ENHANCE ADHESION

LOW TEMPERATURE DEPOSITION RETAINS

NANO CRYSTALLINE CHARACTER OF THE
DEPOSIT

THE VOLMER WEBER ISLAND GROWTH-

CLUSTERING & COALESCENCE
Plasma Enhancement/Assistance

P~10-2 mbar

N-
H+
B+ NH3
Cl- e-
BCl3
B, Cl, N+ Ar+ TO VACUUM PUMP

BN Coating

STEEL SPECIMEN Higher deposition rate

Higher film density
Higher adhesion
HEATER: ~600 deg C Low deposition temp/
NANOCRYSTALLINE
COATINGS
 RF PLASMA SOURCE
RF SUPPLY:
GASFLOW
13.56MHz

M M
A A
G G
N N
E E
T T
I I
C C

F F
I I
E E
L L
D D
M
A

A
S

P
L
 ELECTRON 2.45 GHz ECR
PLASMA,
CYCLOTRON 3kW
Hot stage: 800 deg C
RESONANCE DC/RF BIAS
MW PLASMA COATINGS:
DLC/CNT/DIAMOND
GAS INJECTION:
CH4/H2/Ar

COATING
VACUUM
CHAMBER
WITH 10-3 mbar
Hot stage with BIAS
 PE-CVD REACTOR 2.45 GHz ECR
PLASMA,
ELECTRON 3kW
CYCLOTRON Hot stage: 800 deg
RESONANCE C
MW PLASMA RF BIAS
(2.45 GHz)
COATINGS:
MAGNETIC FIELD 1100 G DLC/CNT/DIAMOND
GAS INJECTION:
CH4/H2/Ar

VACUUM
CHAMBER
COATING
WITH
10-3 mbar
Hot stage with rf /DCBIAS

HIGH VACUUM
EXHAUST GAS/VAPOR
SYSTEM
DELIVERY
WHAT ARE THE MAJOR ADVANTAGES?

LARGE AREA COATINGS

NANO-CRYSTALLINE COATINGS

STOICHIOMETRIC COATINGS

COATINGS EITHER AT ATMOSPHERIC PRESSURE OR AT 10-2

mbar CAN COAT INTERNAL AND ALL SIDES OF A COMPONENT.

OPERATION OF LARGE SYSTEMS WORLD WIDE HAS BECOME A

PRACTICE.

NEARLY ALL TECHNICAL CERAMICS/ METALS/

SEMICONDUCTORS CAN BE COATED.

STOCHIOMETRY AND PRODUCT PURITY ARE GUARANTEED.

COATINGS ARE MOSTLY USED FOR CORROSION AND WEAR

PROTECTION
WHAT ARE THE POSSIBLE COATINGS?
ALL TRANSITION METAL CARBIDES/NITRIDES
( TiN/TiC/ZrN/ZrC/WN/WC/TaN/TaC, SiC, B4C3

BN and Si3N4 and BN

Technical Ceramic like Al2O3, ZrO2, TiO2

LOW PRESSURE CVD DEPOSITED PRESSURE Silicon for

Semiconductor Industry

NANOTECHNOLOGY REVOLUTION:

CNT, DLC, UNCD, TAC

Carbon Nano Tube(CNT)/ DIAMOND-LIKE CARBON/ULTRA

NANOCRYSTALLINE DIAMOND/ GRAPHITE/GRAPHENE/ TETRAHEDRAL
AMORPHOUS CARBON

PLASMA ENHANCED CHEMICAL VAPOUR DEPOSITION- PECVD

WHAT ARE THE VARIANTS OF CVD?
AP-CVD- Atmospheric Pressure CVD—OXIDES COATINGS

LP-CVD- Low Pressure CVD- Device grade Silicon

MO-CVD- Metallo Organic Chemical Vapour Deposition:

NITRIDES/CABIDES/OXIDES

COMBUSTION CVD/FLAME CVD- OXIDES

LASER CVD---LCVD– LOCAL AREA COATINGS

INDUCTION CVD- UDES INDUCTION HEATING TO HEAT THE

COMPONENT

ECR-CVD- Electron Cyclotron Resonance CVD

PE-CVD-PLASMA ENHANCED CHEMICAL VAPOUR DEPOSITION

MW-CVD: MICROWAVE CHEMICAL VAPOUR DEPOSITION

RF- CVD: RADIO-FREQUENCY CVD

HF-CVD: HOT FILAMENT CHEMICAL VAPOUR DEPOSITION
 MECHANISM OF A CVD PROCESS
MOLECULES OF CVD PRECURSOR ( CH4 in
CASE OF CARBON MATERIAL AND ORGANO
METALLIC COMPOUND IN OTHER CASES
ARE USED…

THE MOLECULE GETS ADSORBED ON

ADSORPTION
COMPONENT/SOLID SURFACE

AFTER ADSORPTION THERE WILL BE

DISSOCIATION AND CHEMISORPRPTION

MORE THAN TWO ADSORBATES WILL

CHEMICALLY COMBINE TO FORM COATING SURFACE CHEMICAL
REACTION
IN CASE OF CH4, TWO SIMILAR
ADSORBENTS COMBINE TO FORMA A
COATING
Coating formation and
desorption of organics
THE PRODUCT GAS ( OFTEN FLAMMABLE
AND TOXIC DESORBS .

EXHAUST MANAGEMENT IS A KEY

NECESSITY IN CVD PROCESS
 THE DEPOSITION AND COATING GROWTH RATE IN CVD
Laminar flow

u
d(x)

L dx
THE DIFFUSION CONTROLLED FILM GROWTH RATE IS GIVEN BY FICK S FIRST LAW.

THICKNESS OF THE LAMINAR BOUNDARY LAYER IS GIVEN BY

𝜼𝒙 1/2 𝑳 𝜼 1/2
𝜹 𝒙 = 𝜹= 𝜹 𝒙 𝒅𝒙 = 𝟐𝟑L 𝑻𝒉𝒆 𝑳𝒂𝒎𝒊𝒏𝒂𝒓 𝑹𝒆𝒚𝒏𝒐𝒍𝒅 𝑵𝒖𝒎𝒃𝒆𝒓
𝝆𝒖 𝟎 𝝆𝒖𝑳 𝝆𝒖𝑳
= 𝑹𝒆𝑳 =
𝜼
IN TERMS OF LAMINAR REYNOLD NUMBER,
𝟐𝑳
THE BOUNDARY LAYER THICKNESS TURNS OUT TO BE 𝜹=
𝟑 𝑹𝒆𝑳
THE DIFFUSIVE TRANSPORT FLUX RESPONSIBLE FOR INTERACTION AND
COATING DEPOSITION CAN BE WRITTEN ACCORDING TO FICK S FIRST LAW AS
𝝏𝑪
𝕁 = 𝑭𝑳𝑼𝑿 = −𝔻 𝝏𝒙= - 𝔻
𝚫𝑪 𝜟𝒄
= - 𝔻 𝟐𝑳 𝟑 𝑹𝒆𝑳 L is Characteristic Length
𝚫𝒙
of the System
Gas viscosity , gas density, gas stream velocity U, ReL is Laminar Reynold number
MANY PHASES –ALLOTROPES OF CARBON

(A)Diamond-3D
(B)Graphite-2D
(C)Lonsdaleite
(D)C60- 0-D
(E)C-540-FULLERENE
(F)C-70-FULLERENE
(G)AMORPHOUS
CARBON
(H)SINGLE-WALLED
CARBON NANO
TUBE-CNT-1-D
HIGH PRESSURE PHASE DIAGRAM OF CARBON
VARIOUS HYBRIDIZATION
STATES OF CARBON

-ORBITALS
-ORBITALS

sp3 sp2 sp1

 DIAMOND LIKE
SP3
STRUCTURE

THE CARBON PHASES DIFFER

BY SP3 TO SP2 RATIO

SPUTTERED
AMORPHOUS
CARBON (a-
C:H)
NO CLEAR
COATING
FORMATION
SP2 H

GRAPHITIC CARBON
 DIAMOND FACE CENTERED
CUBIC (FCC) LATTICE WITH sp3
COORDINATION OF CARBON
ATOMS

SPACE GROUP: 𝑭𝒅 𝟑 𝒎
BOTH YELLOW AND
THE INFINITELY TRANSLABLE VIOLET CIRCLES ARE
CRYSTALLINE DIAMOND LATTICE CARBON ATOMS. BLACK
INDICATED OCCUPANCY
SHOWING TETRAHEDRALLY
OF TETRAHEDRAL VOID
COORDINATED CARBON ATOM . IN FCC SUB-LATTICE
THE GRAPHITE LATTICE
Showing stacking of hexagonal planar layers
AND WHAT IS DLC?
A RANDOM AMORPHOUS NETWORK OF CARBON ATOMS HAVING A
COMBINATION OF SP2 AND SP3 BONDED CARBON ATOMS

40% SP2----DLC HARDNESS 25 GPa

20% SP2-TETRAHEDRAL AMORPHOUS CARBON –HARDNESS> 40

GPa

DIAMOND: 100 GPa

Sp2-coordinated
carbon
Sp3-coordinated
carbon
THE DLC NETWORK
DIAMOND OR DLC OR TAC: HOW IT IS FORMED?

SUBPLANTATION / THERMAL SPIKING/ ION BEAM PEENING/ COMPRESSIVE

STRESS GENERATION

MEANS Low ENERGY SUB-SURFACE IMPLANTATION

IN ECR, WITH BIAS DEPOSITION C+ ION ENERGY IS OFF THE ORDER OF 100 eV

THERMAL SPIKE DRIVEN PICOEND TRANSIENT ( >10000° C) SUDDEN PHASE

TRANSFORMATION TO DENSE SP3 DIAMOND PHASE.

HIGH ENERGY IONS PENETRATE THE SURFACE AND FAVOURS SP3 BONDING-
CHARACTARISTICS OF DIAMOND(>8.00eV)----A

NEAR SURFACE ZONES CONTAIN SP2 TYPE OF BONDING(<25 eV)

THE PLASMA DENSITY IN ECR IS 1012/cm3

DLC GROWTH RATE: 1.5 nm /Sec

OVERALL THICKNESS: 2 µm

CONTROLLING GAS FLOW/PLASMA POWER/SUBSTRATE TEMP AND BIAS WE

CAN ENGINEER SP3/SP2 RATIO
WHAT HAPPENS DURING SYNTHESIS OF COATING
BY ECR PLASMA/MW PLASMA ASSISTED CVD

SUB-SURFACE
IMPLANTATION OF
IONS FROM ECR
PLASMA SOURCE
OCCURS
 SUB-PLANTATION ION

MODEL IMPLANTATION
FROM PLASMA

INSERTION OF SURFACE SUB-SURFACE

LAYER OF ATOMS INTO IMPLANTATION
SUB-SURFACE

BURIAL OF FEW MONO-LAYERS COATING

STRESS IS GENERATED DUE TO

INSERTION OF EXTRA ATOMS THAT
GENERATE VACANCY-INTERSTITIAL COMPONENT
PAIR

DENSIFICATION IN THE LOCAL REGION

COMPRESSIVE
DEVELOPMENT OF COMPRESSIVE STRESS
STRESS CAUSES EVOLUTION OF A EVOLUTION
HIGH DENSITY PHASE

A MATHEMATICAL APPROACH FOR SUB-

SURFACE STRESS CALCULATION
BASED ON VACANCY-INTERSTITIAL
PAIR GENERATION IS GIVEN BY SULIN
ZHANG ET AL ( 2003). THIS IS BASED
ON COMPUTER SIMULATION.
 AN EXPRESSION FOR ION IMPLANTATION INDUCES STRESS
THE STRESS GENERATED IN COATING IS COMPRESSIVE IN CHARACTER
F= STEADY STATE DENSITY OF VACANCY –
INTERSTITIAL PAIR FORMED BY ION
𝜶𝑬𝒊 IMPLANTATION
𝟐𝑬𝒅 A= DENSITY OF THE FILM
𝝆𝑭 =𝝆𝑨 𝝋𝑨 𝑬𝒊
/
𝟓 𝟑  and = MATERIAL DEPENDENT COEFFICIENTS
+ 𝜷
𝝋𝑩 𝑬𝟎
Ei= ENERGY OF THE INCIDENT ION

Ed= THRESHOLD ENERGY FOR DISPLACING AN

THE VOLUMETRIC STRAIN THAT ATOM FROM LATTICE SITE
EVOLVES DUE TO INTRODUCTION
OF VACANCIES AND INTERSTIALS E0= ACTIVATION ENERGY REQUIRED TO FORM A
BY ION IMPLANTATION IS VACANCY-INTERSTITIAL ( V-I)PAIR
∆𝑽 𝝆𝑭
𝜺= = 𝒌 i= INCIDENT ION FLUX
𝑽 𝝆𝑨
A= FLUX OF ION ACTUALLY USED IN FORMING
DEFECTS
THE BIAXIAL STRESS THAT
EVOLVES IN COATING IS:
k= RATIO OF RELAXATION VOLUME OF V-I PAIR
TO ATOMIC VOLUME
𝒀 Y= YOUNG S MODULUS
𝝈=
𝟐 𝟏 − 𝟐𝝑  = POISSON S RATIO
REF: SULIN ZHANG ET AL Acta Materialia 51 (2003) 5211–5222
Ultra low friction and high wear resistance of hydrogen and oxygen plasma treated
nanocrystalline diamond nanowire films
As deposited DNW H2 Plasma treated DNW O2 Plasma treated DNW
1.0 µm

Friction coefficient of
0.0001 is obtained for The friction coefficient of
15 minutes H2 plasma O2 plasma treated film
treated DNW films. showed super low value
Such a low valued ~0.002 with high wear
friction coefficient is resistance 2×10–12
described by the mm3/Nm. Presence of
passivation of oxygenated groups on
dangling bonds by surface
hydrogen content and
adsorption of H2O
molecules.

Tribological properties of (a)

as-deposited DNW film and
O2 plasma treatment at (b) 3
minutes and (c) 10 minutes
Science of Advanced Materials 5 (2013) 1–12
 USE OF DLC COATING

WITH A WEAR RATE 10-8 mm3/Nm , IT MAKES AN

EXCELLENT COATING FOR DYNAMIC CONTACTS

ALL ROTATING MEMBERS WHERE GRAPHITE

PROVIDES LUBRICATION, DIAMOND PROVIDES
HARDNESS, DLC MAKES AN IDEAL CHOICES

RECORDED FRICTION COEFFICIENT WITH H: DLC

< 10-2 , IT STANDS OUT AS A LOW FRICTION
MATERIAL SLATED TO SERVE ENERGY
EFFICIENCY.
ENGINEERING CHALLENGES
A comprehensive model to explain
plasma CVD

Explaining sub surface Diamond

synthesis

PHASE FRACTION ( sp3/sp2) control

Precursor for new generation materials

PLASMA CVD FOR C3N4/ Si3N4 based
Nanoscale materials and coatings
QUESTIONS
DISTINGUISH BETWEEN PLASMA CVD AND THERMAL CVD

STATE FUNDAMENTAL PRINCIPLES OF CVD PROCESS? DERIVE

EXPRESSION FOR GAS PHASE DIFFUSIVE FLUX IN TERMS OF
REYNOLD NUMBER?

WHAT APPRACH ONE SHOULD TAKE FOR SYNTHESIZING C3N4

COATING BY CVD PROCESS?

WHAT ARE ALLOTROPES OF CARBON? HOW CAN ONE CONTROL

THEIR FORMATION IN CVD PROCESS?

DESCRIBE PE-CVD REACTOR BASED ON ECR CVD? WHAT ARE THE

PLASMA SOURCES THAT CAN BE USED FOR CVD PROCESS?

HOW IS DIAMOND COATING SYNTHESIZED? DESCRIBE

SUBPLANTATION MODEL. EXPLAIN EXPRESSION FOR
IMPLANTATION INDUCED STRESS BASED ON VACANCY-
INTERSTITIAL PAIR GENERATION

GIVE EXAMPLE OF AN ULTRA LOW FRICTION COATING

SYNTHESIZED BY PE-CVD.
THANK YOU ALL FOR YOUR ATTENTION