HISTORY OF THIN FILMS

GROWTH, TECHNIQUES, CHARACTERIZATION

Pter B. Barna
Research Institute for Technical Physics and Materials Science of HAS
Budapest, Hungary

Autumn School 2005 on Advanced Materials Science and Electron Microscopy

Humbold University of Berlin
Oct. 4th - Oct. 7th, 2005

OUTLINE
Thin films in 20th century
HISTORY OF THIN FILMS
Number of publications dealing with thin films is enormously large,
impossible to review the investigated problems and results,
but the analysis of the

OUTCOME can be tutorial

The main aim of this lecture is to introduce an attempt for synthesizing
a view on the structure evolution of elemental and multicomponent
polycrystalline thin films, which could be considered as the key issue
when thinking about the future of the research and development or even
about the diagnosis of technology.

FUTURE
_____________________________________________________________________
This view is mainly based on the fruitful discussions caried out on this topic
during the last years with Professors J.E. Greene, L. Hultman, I, Petrov and Gy.
Radnczi, as well as with my PhD students Dr. M. Adamik and Dr. A. Kovcs.

Thin films in 20th century:

* kind of material peculiar to condensed phase:
structure can be engineered at atomic level
new properties
* became a basis of advanced technologies, devices and industries
* studied in frame of multidisciplinary research
vacuum science
solide state physics and chemistry
surface science
crystal growth
statistical/computational physics
adavanced characterization methodes
"Just as rapid advances in vacuum technology were necessary to launch the
modern era of thin film technology, it was the phenomenal growth of surface
science and applications, together with the continued development and
increasing availability of high resolution transmission electron microscopy,
that allowed the emerging field of thin films to slowly evolve from a highly
advanced empirical art, driven by a very real set of economic and social
benefits, toward an identifiable field of science."
(J.E. Greene, J. Vac. Sci. Technol., A 21(2003)S71)

HISTORY
End of 19th century - unusual properties of deposits on the walls of glass discharge tubes
erosed interest of researchers: optical&electrical properties (P. Drude, Ann. der Physik, 36(1889)532)
1927:

- electron diffraction on thin films (Davison - Germer)

1930th1940th

- practical application: high reflectivity surface mirrors on non- conducting substrates

- vacuum and thin film (PVD) techniques, devices;
- electron microscopy (Ruska);

1960th-

- in situ electron microscopy (Bassett, Pashley, Poppa, Pcza, Honjo) ;

- surface decoration (Bassett, Bethge, Distler);
- ultrahigh vacuum technique;
- surface analytical methodes: Auger spectroscopy, LEED, SEM, ESCA;
- structure zone model: compilation of experimental results (Movchan-Demchishin)

1970th -

- high resolution (also surface imaging) and analytical TEM ( Halle School);
- chemical vapour deposition (CVD);
- computer simulation: atom-by-atom structure building (Gilmer&Bennema,
Barna,Thomas et al; Dirks&Leamy)
- molecular beam epitaxy (MBE);
- CERMET (nanocomposite) resistor films (Neugebauer);

1980th -

- atomic resolution surface imaging techniques: STM, AFM (Binning&Rhrer)

- atomic layer epitaxy;
- electron energy loss analysis - dedicated scanning TEM;

1990th

- aberration corrected ultrahigh resolution analytical TEM (Urban);

2000th

- advent of in situ techniques (UHV TEM, fast STM, synchrotron)

The pioneering reviews - books

W. Espe and M. Knoll: Werkstoffkunde der Hochvakuumtechnik,(1936)
S. Dushman: Scientific Foundation of Vacuum Techique, (1949)
H. Mayer: Physik dnner Schichten, Teil I (1950) und II (1955)
O. S. Heavens: Optical Properties of Thin Films (1955)
L. Holland: Vacuum Deposition of Thin Films, (1956)
M. Auwrter: Ergebnisse der Hochvakuumtechnik und der Physik dnner Schichten, (1957)
K. L. Chopra: Thin Film Phenomena, (1969)
L. I. Maissel, R. Glang: Handbook of Thin Film Technology, (1970)
H. Mayer: Physics of thin films Parts, I and II, (Complete bibliography), (1972)
B. Lewis, J.C. Anderson: Nucleation and Growth of Thin Films (1978)
Remark: the book of B. Lewis, J.C. Anderson is a comprehensive rewiev of the results on the
elementary processes of structure formation revealed partly by in situ TEM experiments.

OUTCOME
Development of
a resource of scientific knowledge on

preparation, structure evolution and structure - property causality of thin films

*

advanced and sophisticated thin film preparation devices

and methods based on advances in vacuum technology

advanced characterization devices and methods

as a consequence of these
THIN FILMS HAVE TAKEN A PROMINENT PART in
* revolutionary development of new active and passive elements,
devices and industries;
* metamorphosis of society to "information society"

TOPICS OF INVESTIGATIONS AND THE CAUSALITY

Important aspect of technology: evolution of the material structure
TECHNOLOGY
TECHNOLOGY
PREPARATION
PREPARATIONMETHOD
METHOD
- -material(s)
material(s)
- -source
source
- -parameters
parameters

TECHNOLOGY
TECHNOLOGY
STRUCTURE
STRUCTUREEVOLUTION
EVOLUTION
self
selforganizing
organizingprocess
process
controlled
controlledby
bytechnology
technologyparameters
parameters
- - nucleation
nucleation
- - crystal
crystalgrowth
growth
- - grain
graingrowth
growth - -restructuring
restructuring
- - surface
surfacechemical
chemical interactions
interactions
- - phase
phaseformation,
formation,transformation
transformation

Relationships investigated generally

Relationships to be understood
for tailoring film

APPLICATION
APPLICATION

PHYSICAL
PHYSICALand
andCHEMICAL
CHEMICAL
PROPERTIES
PROPERTIES

STRUCTURE
STRUCTURE
phase
phasestate
state
morphology
morphologyofofgrains
grainsand
and
surfaces
surfaces
structure
structureofof crystals
crystals
orientation
of
orientation ofcrystals,
crystals,texture
texture
chemical
composition
chemical composition
homogeneity
homogeneity
substrate
substrate- -film
filminterface
interface

Causality
Route of tailoring

The main aspect of thin film technology is that the "self

organizing" structure evolution takes place
by an atom-by-atom adding process
at temperatures far from thermodynamic equilibrium
which allow the controlled synthesis of
metastable phases
artificial structures: multilayers, nanocomposites
Further possibility to control the structure evolution and structure is the codeposition of minute amount of active additives, an example: aluminium
deposition

Tailoring of nanocomposite structures by codepiting inhibitor additive

Physically separated microcrystals in
CoCrTa recording media (Sinclair, 1992)

Cross-section

In-plane

FePt recording media doped with SiO2 (Sfrn et.al. Thin Solid Films, in print)

cross section

Operation of oxygen as
inhibitor additive at the
deposition of Al films
Grain morphology and
texture of Al films deposited
at TS = 0,3 Tm
as a function of

Koxygen = Joxygen/JAl
the incident Oxygen (Joxygen)

to

Aluminium (JAl)) flux ratio

P.B. Barna, M. Adamik, Thin Solid Films,
317(1998)27

STRUCTURE EVOLUTION
self organizing process

realized in
fundamental phenomena

can be described by the

pathway of structure evolution
course of the fundamental phenomena

related to thermally activated

atomic processes

temperature dependence
nucleation
adatom migration

derived
structure zone models

crystal growth
adatom self surface diffusion

basis for the evaluation

of experimental results

grain growth
bulk diffusion
P.B. Barna, M. Adamik, Thin Solid Films, 317(1998)27; I. Petrov, P.B. Barna, L. Hultman, J.E. Greene, J.
Vac. Sci. Technol.,21(2003)S117)

Fundamentals of the self organising nature of thin film

growth
STRUCTURE EVOLUTION
self organizing process

controlled by

determined by the
concrete
structural
conditions
at any instant
structural
preconditions

- electronic structure of

constituent atoms
types of crystal structure
- thermodynamics

- kinetics
phase state
material structure

TECHNOLOGY
PARAMETERS

Role of kinetics: diffusion-limited two-dimensional aggregation of atoms

Au deposition on Ag(111)
M. Klaua, Proc. 2nd Colloqium
on Thin Films, ed. E. Hahn,
Budapest, 1967, p. 152.

a-Ge islands grown on cleaved NaCl (100) surface. Computer

simulation of growth on a square lattice considering limited edge
diffusion (D1) (A.Barna, P.Thomas, et al., Thin Solid Films, 48, (1978) 163)

Variation of
the shape
with the edge
migration
distance (D1)
of adatoms:
a) D1 = 0
c) D1 = 4
f) D1 = 8

DISCUSSION IS FOCUSSED on
* fundamental phenomena and path-way of structure
evolution
which can make possible
- to understand

* the formation mechanisms of various structures

* operation of additives/contaminants
* interpretation of experimental results
- tailoring designed structures to achieve the specified properties
- selection and tailoring the adequate preparation method and
parameters
- diagnosis of thechnolgy
aspects and problems of the preparation of thin film structures by
simulation and physical experiments

"Crystal growers have been moving inexorably closer to being able to deposite
layers and hence to control film properties on an atom-by-atom basis. We

nearing an era in which it will be possible to deposite

"designer" materials with a specified set of properties."
(J.E. Greene, MRS Bulletin, 26(2001)777)

are

Types of thin films and preparation modes

mono crystal

polycrystal

amorphous

elemental
mono phase

multicomponent
mono or poly phase

prepared by

prepared by

MC/MD simulation
physical experiments

(MC/MD simulation)
physical experiments

contamination

contamination
deviation from
stoichiometry

Aspects and problems of the preparation of thin film

structures by simulation and physical experiments
Preparation by simulation experiments:
Kinetic Monte Carlo (MC) and molecular dynamic (MD)
- related to idealized systems: species, building the structure, are known
- present direct insight into the behaviour of adatoms and atomic interactions
- but: high amount of data of activation barriers are required
- crucial is the knowledge of the correct potentials
source

Preparation by physical experiments:

conditions are far from idealized system:
contamination

material

- substrate contamination ( bulk, adsorbed gases)

- deposition takes place in an environment:

enviroment

co-depositing environmental impurity species (mostly

not controlled and known)
substrate

Effect of contamination on the nucleation density and orientation of

Au crystals on NaCl cleaved surfaces
carbon contamination of the surface
developed during heat treatement of
NaCl: affected: nucleation density and
orientation

dependence of Au nucleation density on the

level of contamination during deposition
M.Kroh, H.Bethge, Thin Solid Films, 57(1979)227

M. Krohn, . Barna, Proc. 2nd Colloqium on Thin Films,

ed: E. Hahn, Akadmiai Kiad, Budapest, 1967, p.45

clean

contaminated

Krohn-Bethge
high purity
deposition

[111]

[001] + random

Effect of additives on the monolayer growth: epitaxial Pt film

(Poelsema et al.: Acta Phys. A, 53(1991)369)

Effect of oxygen on the surface growth morphology of Al films (TS = 3000 C)

(Barna et al.: phys. stat. sol. a., 55, (1979) 427 )

truncation by step bunching

Kox~10-3

Kox~10-2

Kox>10-1

Kox~ 10-3

Effect of CO adsorption on the growth of Pt on Pt(111) surface at 400 K

(M. Kalff, G. Comsa, Th. Michely, PRL 81(1998)1255)

(STM topograhs, scan size 1700 X 2500 .)

Parcial pressure of CO during deposition, mbar

< 5x10-12
"clean"

"In

1x10-10

4.7x10-10

9.5x10-10

1.9x10-9

conclusion, we have demonstrated that all aspects of homoepitaxial growth

on Pt(111) are influenced by minute amounts of adsorbed CO."

Conclusions on impurity effects

" Experiencing the development of unusual structural features one has to search for contamination
effects, at first." (P.B. Barna, Proc. 9th International Vacuum Congress, Madrid, 1983, p. 382)

"when reactive surfaces are under study, data from apparently well-characterized
samples may be governed by contaminant effects. The reason is that gas species
from the ambient tend to adsorb at defects, such as island edges, where their effects are
likely to be particularly large. When this is the case, it is unclear what inferences to
draw from agreement of simulations with experiment."
(P. J. Feibelman, PR B 60(1999)4972.

"The experiments presented indicate also that in order to obtain results representative
for a clean growth system, impurity atom to deposit atom impingement rates
(Kimp/dep = Nimp/Ndep) of 10-4 or below may be necessary. This is substantially less
than previously anticipated." (M. Kalff, G. Comsa, Th. Michely, PRL 81(1998)1255)

That means: for clean system at 1 monolayer/s deposition rate the

total pressure of active gases in the preparation system ( e.g. water
vapour, oxygen, CO, etc.) should be less than 10-10 Pa.

Advanced systems make

possible comprehensive
investigation of thin film
growth processes

Schematic diagram of a
computer-controlled
multichamber UHV gassource molecular-beam
epitaxy system
(J.E. Greene, MRS Bulletin, 26(2001)777,)

Fundamental phenomena and path-way of structure evolution

elemental system: growth of high purity indium film at Ts = 0,6 Tm,
(UHV in situ TEM experiment, J.F.Pcza, Proc. 2nd Coll. on Thin Films, Budapest, 1967)

The elementary atomic processes and related fundamental phenomena of

structure formation operating in various stages of film growth (elemental film, TS> 0,3Tm)
GROWTH
STAGES

atomic processes
FUNDAMENTAL PHENOMENA

NUCLEATION

migration of adatoms on substrate

CLUSTERING/NUCLEATION primary

ISLAND
GROWTH

self surface diffusion

CRYSTAL GROWTH on substrate
NUCLEATION primary

COALESCENCE 1

COALESCENCE 2
CHANNEL GROWTH

THICKNESS
GROWTH
(P.Barna, in Diagnostics and Application of thin films,
Ed. L. Eckertova, I. Ruzicka, IOP, 1992, p.295)

self surface diffusion

CRYSTAL GROWTH
bulk diffusion
COALESCENCE TYPE I complete
NUCLEATION secondary
self surfce diffusion
CRYSTAL GROWTH
bulk diffusion
COALESCENCE complete/incomplete
GRAIN GROWTH abnormal
NUCLEATION secondary
self surface diffusion
CRYSTAL GROWTH
bulk diffusion
GRAIN GROWTH abnormal/normal

PATH-WAY of STRUCTURE EVOLUTION of ELEMENTAL FILMS in range TS 0,3 Tm

(P.Barna, in Diagnostics and Application of thin films, Ed. L. Eckertova, I. Ruzicka, IOP, 1992, p.295)
STAGES of STRUCTURE EVOLUTION
PHENOMENA

NUCLEATION

STRUCTURAL PRECONDITIONS
active in the next growth stage

SUBSTRATE
CLUSTERS NUCLEI random, random

CRYSTAL GROWTH on substrate

COALESCENCE
complete
t y p e I liquid like
secondary nucleation
t y p e II
incomplete
CRYSTAL GROWTH and
GRAIN GROWTH in polcrystalline matrix

INDIVIDUAL SINGLE CRYSTALS

primary- random, secondary- random

INDIVIDUAL SINGLE CRYSTALS

random
texture
random
texture
POLYCRYSTALLINE ISLANDS
RESTRUCTURING
texture
CHANNELS

secondary nucleation
FILLING THE CHANNELS
CRYSTAL and GRAIN GROWTH

CONTINOUS POLYCRYSTALLINE
texture

AS-GROWN STRUCTURE
columnar, polycrystalline
uniform grain size - texture in cross section
GB-s: perpendicular to the film plane

DERIVATION of the STRUCTURE ZONE MODEL of elementary thin films

growing on amorphous substrate

thickness

random

competitive growth texture

restructuring growth texture

grain growth (abnormal)

crystal growth

(crystal growth) crystal growth (competitive)

nucleation
nucleation
Zone I
Zone T
0,1
0,3

adatom migration
on substrate

nucleation
Zone II

adatom migration
on substrate

adatom migration
on substrate

self.surf.diff.

self. surf. diff

(very limited)

self.surf.diff.
(very limited)

bulk diffusion
GB migration

TS/Tm

STRUCTURE EVOLUTION IN ZONE T: COMPETITIVE GROWTH OF

Aluminium CRYSTALS ON AMORPHOUS SUBSTRATES at TS= 100K
(Simulation experiment: F.H.Bauman, D.L.Chopp, T.Diaz de la Rubia, G.H.Gilmer, J.Greene,
H.Huang, S.Kodanbaka, P. OSullivan, I.Petrov, MRS Bulletin, 26 (2001) 182)

(111) crystals, (100) crystals

oo1 oriented crystals of low diffusivity (low potential energy) grow faster
than 111 oriented ones of high surface diffusivity (high potential energy)
Characteristic for Zone T: coalescence (grain growth) does not operate
On amorphous substrates nuclei are randomly oriented, growth competition
takes place among the crystals of various orientation during film growth
developing V-shaped columns and changing texture with film thickness
(competitive growth texture).

ZONE T structur in TiAlNC coating grown on oxidized Si substrate

V-shaped columnar morphology and competitive 111 growth texture

flat - smooth surface

111 texture

FFT

random

competitive growth texture

restructuring growth texture

Conclusions on structure evolution in elemental thin films

* correlation exists between grain size, grain morphology, surface
topography and texture, these are developing together
* the in-plane size (column diameter) and the orientation of crystals
can be controlled by the temperature
* the as-deposited structure has low thermal stability
* the possible zones are: Zone I, Zone T and Zone II
* in Zones I and II the structure and orientation are uniform along
thickness, crystals penetrate through the film
* no grain boundaries parallel to the substrate, i.e. no equiaxed grain
morphology (Zone III ) can exist
that means: %

conventional structure zone models compiling experimental results

are realted to systems contaminated by inhibitor impurity:
Zone III is present
Movchan-Demchishin
1969

Messier et. al
1984

Thornton
1974

Grovenor et. al
1984

Fundamental phenomena and path-way of structure evolution

two component system: growth of carbon doped indium film, Ts = 0,6 Tm,
(in situ TEM experiment, Pcza et al., Jpn. J. Appl. Phys., Suppl. 2, Part 1.(1974)525)

Nucleation and competitive growth of constituent's phases composition: A1-xBx,

x<0,1 : limited mutual solubility, no reaction phase of A1-xsBxs
constituent A: majority
component
constituent B: additive
composition: A1-xBx, x<0,1

primary nucleation
of A,
segregated

Bpecies adsorbed
adatoms on the
growth surface of
primary phase A

delayed
nucleation of
secondary
phase B on
growth surface of
primary phase A

B or A1-xsBxs phases are growing in 2D surface

covering layer : tissu phase, inhibitor additive,

B or A1-xsBxs phases are growing in 3D

inclusions

Tailoring of TiN structure by codepositing Si

Modfel of TiSiN nanocomposite

structure,
S. Veprek, Thin Solid Films 297(1997)145

3 nm
Changes of TiN structure with increasing Si concentration
J. Patscheider, Th. Zehnder, M. Diserens, Surf. Coat. Technol., 146-147(2001)201

STRUCTURE ZONE MODEL of oxygen doped aluminium film

(P.B. Barna, M. Adamik, in Protective coatings and thin films, (Eds. Y. Paulea, P.B.Barna, Kluver 1997, p.279)

The conventional and the derived structure zone models

conventional

derived
effect of inhibitor additive

Movchan-Demchishin
1969

Messier et. al
1984

Thornton
1974

Grovenor et. al
1984

Barna-Adamik, 1988

3-D INCLUSIONS DEVELOPED IN CO-DEPOSITED FILMS

Al-Pt (2 at%)

Al6Pt as secondary phase

A.Kovcs et al., Proc. ICEM15,
Durban SA, 2002, p.687

Al-Ni (5 AT%)

P.B.Barna, in L.Eckertova, T Ruzicka,

Diagnostics and Applications of Thin Films,
IOP 1992, p.295

Conclusions
(P.B. Barna, M. Adamik, Thin Solid Films, 317(1998)27; I. Petrov, P.B. Barna, L. Hultman, J.E. Greene,
J. Vac. Sci. Technol.,21(2003)S117)

The structure evolution in polycrystalline films (both elemental and

multicomponent) can be described by a pathway (characteristic for every
materials system) on the basis of the same fundamental phenomena of
structure formation:
nucleation, crystal growth, grain growth
The operation of every single fundamental phenomenon is related to a thermally
activated atomic process (temperature dependence of the pathway)
The atomic processes are:
adatom diffusion (Ts > ~ 0,05Tm) (nucleation)
self surface diffusion (Ts > ~ 0,1Tm) (crystal growth, coalescence)
bulk diffusion (Ts > ~ 0,3Tm) (grain growth)
in multicomponent films additionally:
chemical interaction among species
including
process induced segregation of excessive pecies
resulting in
delayed nucleation of secondary phase(s)

FUTURE
Combination of dedicated physical and simulation experiments at carefully
designed conditions with special attention to possible contamination effects
Dedicated experiments on model material systems for collecting data on the
elementary atomic processes (surface and bulk) controlling the cours of the
fundamental phenomena of structure formation
Comprehensive causality analysis of preparation-structure-properties
Comprehensive structure analysis (bulk and surface) at atomic resolution
Extended application of in situ and combinatorial experimental methods