Tailoring thin films for catalysis:

Thin Film Growth Methods and Properties

Rutger Schlatmann

Division Head Solar Energy and Project leader Catlab @Helmholtz-Zentrum Berlin

Thanks to Florian Ruske (HZB) and Steffi Hlawenka (HZB)

Catlab Lectures Program 2023/2024

2
Catlab Lectures Program 2023/2024

3
 AGENDA

1. Motivation

2. Methods, focus on vacuum based

• Physical Vapor deposition

• Chemical Vapor deposition
3. Film growth
• Growth parameters and properties
• From adsorption to incorporation
• Film nucleation and structure
4. Examples with relevance for catalysis
research
• GaN blue LED Thin film (CIGS) solar cell cross section
© HZB/P.
Note: Dera
Colors are artificial!
• PV: Thermal and electronic control HZB
• PV: Optical and electronic control

4
 1. MOTIVATION

No energy transistion without massive electrification

enabled by photovoltaics (and wind, batteries and…)

Science 2023 (10.1126/science.adf6957 )

5
 1. MOTIVATION

No energy transistion without chemical energy carriers

*Data based on IEA World Energy Balances Highlights 2021,
"Heat" includes electricity used for heating. Low temperature
processes
(below 150 °C)

Intermediate
temp. processes
(150 - 400 °C)

High temperature
processes
Global energy demand* Global industrial heat demand* (above 400 °C)
~116 000 TWh/a ~30 000 TWh/a

Sustainable global energy system relies on tremendous Processes for production of

building blocks of society
• expansion of renewable electricity capacity (steel, cement, paper, glass,
• power-to-heat technology implementation plastics,…) require use of
chemical energy carriers
• sustainable production of chemical energy carriers for
energy transport and high-temp processes 6
 1. MOTIVATION

No chemical energy carriers without catalysis

Hydrogen and its derivates as key building block of a sustainable energy system

7
 1. MOTIVATION

No chemical energy carriers without catalysis

Hydrogen and its derivates as key building block of a sustainable energy system

Conventional catalysts:
• not sufficently
understood, therefore
difficult to optimize
• based on expensive and
rare materials
• require reactors heated
by burning fossil fuels

8
 1. MOTIVATION

No chemical energy carriers without catalysis

Hydrogen and its derivates as key building block of a sustainable energy system

Novel catalysts:
• Based on thin-film and
nanotechnology
• Studied by advanced
(operando) techniques
• Adaption of reactors
regarding usability of
renewable electricity

Tailor-made, energy, material and cost efficient catalysts

using functionalized thin films
9
 1. MOTIVATION

Thin film technology is well established

Chemical - Corrosion resistance
- Diffusion barriers
- Catalytic coatings
Mechanical - Scratch protection, Hardness
- Adhesion, wetting behavior
Optical - Light Emitting Diodes (LEDs)
- Reflective / antireflective
- Decorative, filters
- Optical memory, waveguides
Electrical - Batteries, insulators, conductors,
semiconducting devices, piezoelectrics
Magnetic - Memory devices (cassettes, disks)

Thermal - Architectural glazing, barriers, heat sinks

10
 1. MOTIVATION

THIN-FILM TECHNOLOGY IN PHOTOVOLTAICS

Thin-film deposition technologies

are crucial for all modern solar cells Ag grid Ag grid
(PERC, TOPcon, Silicon SiNx
(n)c-Si
TCO
(p)a-Si (5-10 nm)
Heterojunctions and … thin film PV (i)a-Si (5-10 nm)

Global 2022 PV market >200 GWp, at n-Si

20% module efficiency this
corresponds to 1000 km2 of coating (i)a-Si (5-10 nm)
(n)a-Si (10-20 nm)
AlOx/SiNx TCO
Deposition technology determines if Ag + local BSF
Ag (100-200 nm)

performance, material consumption PERC Si Heterojunction

and cost can be reached.
Same will apply for thin film
catalysts.

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 1. MOTIVATION

HIGH-EFFICIENCY TANDEM SOLAR CELL MADE @ HZB

Silver (100nm; Thermal evaporation)
Anti-reflective coating (100nm; Thermal evaporation)
IZO (100nm; Sputtering)
SnO2 (20nm; ALD)
C60 (20nm; Thermal evaporation)
Perovskite (400-600nm; Spincoating)
SAM (Self-assembled monolayer; 1nm; Spincoating)
ITO (20nm; Sputtering)
nc-SiOx:H (n) (95nm; PECVD)
a-Si:H (i) (5nm; PECVD)
c-Si (n) (270µm) Al-Ashouri, A., Köhnen, E., et al. (2020). Science
https://doi.org/10.1126/science.abd4016
a-Si:H (i) (5nm; PECVD)
a-Si:H (p) (5nm; PECVD) Mariotti, S., Köhnen, E., et al. (2023). Science
AZO (120nm; Sputtering) https://doi.org/10.1126/science.adf5872
Silver (400nm; Sputtering)

World record solar cells by tailoring material composition and

opto-electronic properties of thin films AND their interfaces 12
 1. MOTIVATION

SPUTTER COATER FOR INSULATING ARCHITECTURAL GLASS

Ag Blocker
SnO2
ZnO
Glas TiO2

Sn
O
2 c
t
blo ran ov
s er
ck pa
ing re
Ag lay nt
(1 er
2n
m
)

13
 1. MOTIVATION

PANEL SIZE IN DISPLAY

PRODUCTION
A development
of approx. 15
years

SIVApower 14
 1. MOTIVATION

SUMMARY: MOTIVATION
• Thin film technology allows specifically tailoring
material composition and properties for certain
applications, objects or conditions

• Can be used on a variety of surfaces or conditions to

alter their properties (Chemical, Mechanical, Optical, 0 × 3 0 cm²
3
Electrical, Magnetic, Thermal)

• Technology can be applied for catalytic applications 5.7 / 1.4 m²

15
 2. METHODS

2. METHODS

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 2. METHODS

COATING METHODS
Methods to Manufacture Thin Films on Substrates

Chemical Vapor Deposition (CVD) Physical Vapor Deposition (PVD) Others

Thermal ALD PECVD Sputtering Evaporation Spin Coating of Sol-Gel

APCVD
Thermal Plasma LPCVD DC AC Magnetron Electroplating Printing

Thermal PLD Electron Beam Screen Printing Inkjet

§ CVD & PVD: deposition of film from gas phase („V“ = vapor)
§ CVD: precursor material is gaseous, chemical reaction on or near substrate for film growth
§ PVD: precursor material vaporized by physical means, condensation on substrate 17
 2. METHODS

MAIN DEPOSITION TECHNIQUES AT HZB (NOT COMPLETE)

Chemical Methods Physical Methods

Chemical bath Evaporation Sputtering Pulsed Laser

Electrodeposition • Thermal • Magnetron Spin coating

• Electron beam • Reactive
• Ion beam Ink jet
Chemical Vapor Deposition
Screen
Atomic Layer Deposition printing

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 2. METHODS
WHAT IS VACUUM?
coarse
10-9 ultrahigh 10-6 high 10-3 fine 1
pressure (mbar)
Vacuum = region with gaseous pressure < atmospheric pressure

p × V = N × kB × T
Ideal gas law
1 m3
20 °C
p pressure
V volume
N number of particles
kB Boltzmann constant
T temperature

-> Ultra-clean conditions

-> No heat conduction

19
 2. METHODS
MEAN FREE PATH
coarse
10-9 ultrahigh 10-6 high 10-3 fine 1
pressure (mbar)
§ Mean free path (λ) = distance a particle travels between two
collisions with other particles
λ
§ Rule of thumb p × λ = const.

gas const. (mbar m) p (mbar) λ

He 17.5 × 10-5 10-8 17.5 km
H2 O 6.8 × 10-5 10-8 6.8 km
Xe 3.6 × 10-5 10-8 3.6 km
any 5.0 × 10-5 103 50 nm
(for estimation) 100 50 µm
10-8 5 km
https://www.pfeiffer-vacuum.com/en/know-how/introduction-to-vacuum-technology/fundamentals/mean-free-path/ 20
 2. METHODS
COVERAGE TIME
coarse
10-9 ultrahigh 10-6 high 10-3 fine 1
pressure (mbar)
Coarse vacuum (λ < chamber) -> gas particles collide mainly with each other

High & ultrahigh vacuum (λ > chamber) -> gas particles collide mainly with walls

Reflection at wall in every direction possible

Particles may also adhere on wall forming a film

τ (s) = 3.2 × 10-6 / p (mbar)

Coverage time (τ) = time to form p (mbar) τ (s)
10-3 3.2 ms
monolayer on bare surface,
10-6 3.2
rule of thumb:
10-9 53 min
10-11 88 h

21
 2. METHODS
SELECTED DEPOSITION METHODS

Methods to Manufacture Thin Films on Substrates

Chemical Vapor Deposition (CVD) Physical Vapor Deposition (PVD) Others

Thermal ALD PECVD Sputtering Evaporation Spin Coating of Sol-Gel

APCVD
Thermal Plasma LPCVD DC AC Magnetron Electroplating Printing

Thermal PLD Electron Beam Screen Printing Inkjet

§ CVD & PVD: deposition of film from gas phase („V“ = vapor)
§ CVD: precursor material is gaseous, chemical reaction on substrate for film growth
§ PVD: precursor material vaporized by physical means, condensation on substrate

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 2. METHODS

(ULTRA) HIGH VACUUM EVAPORATION

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 2. METHODS
TYPES OF EVAPORATION

thermal electron beam pulsed laser

Laser
laser

-
electron

e
beam beam
heater
target material film substrate

in equilibrium in non-equilibrium

High energy sources (electron beam, laser beam) used for high-melting materials

Local heating in cold crucible -> less contamination from crucible compared to
thermal

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 2. METHODS

RATE OF EVAPORATION DEPENDS ON TEMPERATURE

Rate of evaporation depends on energy of

particles, i.e. temperature.
T low T high
evaporated particles need enough energy to overcome
Probability that a particle has energy E -> binding energy
Maxwell-Boltzmann (MB) distribution

Average energy of evaporated particles (=

maximum MB distribution) = 3/2 kT f(E): probability that a particle has energy E
k: Boltzmann constant
T: temperature

Mean free path and thus vacuum

conditions crucial
25
 2. METHODS
THERMAL EVAPORATION OF ALLOYS
§ Alloys difficult to evaporate from one source due to different vapor pressures of
the elements
§ Example: Evaporation of BaTi films from BaTiOx target
§ Vapour and deposited films initially almost pure Ba
§ Composition of deposited film slowly drifts towards enriching by Ti

vapor pressure (Pe) (torr)

temperature (°C)
Södervall, Chalmers University 26
 2. METHODS
PULSED LASER DEPOSITION

Focused high power laser strikes target of desired composition

Non-equilibrium due to extremely short laser pulses -> flash of evaporants

Composition of deposited film identical to that of target

Wang 2013, Laser Based Fabrication of Graphene 27
 2. METHODS

SUMMARY HIGH VACUUM EVAPORATION

• Thermal evaporation is the basic physical vapor deposition process, requires

good vacuum for accurate layer composition control
• Relatively simple in case of metal films (e.g. metal coatings for food packaging)
• Relatively poor adhesion and low damage to substrate,
• Evaporation of alloys is usually quite complex
• E-beam evaporation for high melting point materials
• Pulsed Laser Deposition for complex materials

28
 2. METHODS
SELECTED DEPOSITION METHODS

Methods to Manufacture Thin Films on Substrates

Chemical Vapor Deposition (CVD) Physical Vapor Deposition (PVD) Others

Thermal ALD PECVD Sputtering Evaporation Spin Coating of Sol-Gel

APCVD
Thermal Plasma LPCVD DC AC Magnetron Electroplating Printing

Thermal PLD Electron Beam Screen Printing Inkjet

§ CVD & PVD: deposition of film from gas phase („V“ = vapor)
§ CVD: precursor material is gaseous, chemical reaction on substrate for film growth
§ PVD: precursor material vaporized by physical means, condensation on substrate

29
 2. METHODS

BASIC PRINCIPLE OF SPUTTERING (KATHODENZERSTÄUBUNG)

-
cathode
target (glued to cathode)
U0
Ar+ ions
substrate
anode
+

§ DC voltage (U0) applied across two electrodes -> breakdown electric field
surpassed and plasma created -> positive Ar+ ions accelerated toward target -> Ar+
ions vaporize target material & releases secondary electrons -> vapor condenses
on substrate -> film growth
§ 99 % of released target particles neutral
§ Typical process conditions: p = 10-1 mbar, U0 = 3000 V, IAr+ = 1 mA/cm2
30
 2. METHODS

„GLIMMLICHT“ AND „DUNKELRAUM“

-
target electrode / cathode
target
U0 „Dunkelraum“
„negatives Glimmlicht“
substrate
substrate electrode / anode
+

§ Secondary electrons accelerated toward anode -> excite and ionize more Ar atoms
§ Ar+ atoms return to equilibrium by emitting a photon -> „negatives Glimmlicht“
§ „Dunkelraum“: region where electron energy not sufficient to excite Ar atoms

31
 2. METHODS

MAGNETRON SPUTTERING

§ Magnetic field established at target electrode by magnets

§ Magnetic field increases electron trajectory -> enhanced ionization efficiency
§ Higher deposition rates possible, but inhomogeneous target usage!
2. METHODS

SPUTTERING CHAMBER IN OPERATION

33
 2. METHODS
PARASITIC PROCESSES

secondary electrons
(13 %)

ejected atoms
(2 %)

heat (85 %)

Implantation of Ar+ (ion tracks and number of implanted ions depend on ion mass and
energy, target mass, impact angle)

Reflection of Ar+

Heating of target material -> cooling needed! 34

 2. METHODS

COLLISION CASCADES IN SPUTTER TARGETS

• Energy transfer to solid causes high energy collision within a certain volume below the target
surface.
à A collision cascade is formed.
• In the collision cascade the primary energy (of the ion) is distributed onto a number of atoms.
• Collision cascades have dimensions of a few 10 nm.
• Approximately 1000 atoms are involved in a collision cascade.
• If enough momentum (energy) is transferred to a surface atom, these can overcome the
binding energy and are emitted as sputtered particles.
• Approximately 99 % of the sputtered particles are neutral!
• Approximately 85 % of the energy is converted to heat, 2% to the desired ´ejected´ atoms

35
 2. METHODS

SIMULATION OF COLLISION CASCADES IN TARGET

calculated calculated

Primary energy distributed among more than 1000 target atoms

Surface atoms escape if incoming ion energy >> binding energy of target atom
36
 2. METHODS

SPUTTERING YIELD & ENERGY DISTRIBUTION

sputtering yield

energy of
incoming ions

threshold

10 to 30 eV
energy of incoming ions Epeak

§ Less than 10 - 30 eV not sufficient to release target atoms (sputtering yield = 0 %)

§ Energy distribution [ΔN/ΔE(E)] follows „Thompson-Distribution“, most released
target particles have several eV of kinetic energy: One to two orders of
magnitude more than for thermal evaporation!
37
 2. METHODS

SUMMARY SPUTTERING
• Sputtering is a very widely used industrial process for physical vapor deposition
process
• High versatility in target preparation, also for more complex materials such as
alloys and oxides
• Relatively good adhesion and higher damage to substrate
• AC sputtering for non-conductive target materials
• Magnetron sputtering for both DC and AC methods to increase deposition rate

38
 2. METHODS

SELECTED DEPOSITION METHODS

Methods to Manufacture Thin Films on Substrates

Chemical Vapor Deposition (CVD) Physical Vapor Deposition (PVD) Others

Thermal ALD PECVD Sputtering Evaporation Spin Coating of Sol-Gel

APCVD
Thermal Plasma LPCVD DC AC Magnetron Electroplating Printing

Thermal PLD Electron Beam Screen Printing Inkjet

§ CVD & PVD: deposition of film from gas phase („V“ = vapor)
§ CVD: precursor material is gaseous, chemical reaction on substrate for film growth
§ PVD: precursor material vaporized by physical means, condensation on substrate

39
 2. METHODS
BASIC PRINCIPLE

inlet exhaust

precursor
(e.g. gas)

deposited film

• Deposition by reaction of one or more precursor

materials from gas phase onto substrate.

• Reactions can be complex, mostly central atoms are transported to the

substrate while ligands end up in the exhaust gas line.

• Precursor gases sometimes transported by carrier gas (e.g. N2)

• Broad spectrum of materials can be deposited by CVD

Conductors (Cu, W, Al, MoSi2, doped Si, transparent conductive oxides)

Semiconductor materials (Si, Ge, GaAs, AlGaAs, InO, GaOnP, ZnS, CdTe…)

Dielectrics (SiOx, SiNx, SiOxNy, TiOx, …)

40
 2. METHODS

OVERVIEW OF CVD TECHNIQUES

LP-CVD Low-Pressure CVD
AP-CVD Atmospheric-Pressure CVD
PE-CVD Plasma-Enhanced CVD
MO-CVD Metal-Organic-CVD
MP-CVD Microwave Plasma-Assisted-CVD
PE-CVD
HW-CVD Hot-Wire-CVD
1500 °C VD
RT-CVD Rapid-Thermal-CVD LP
-C

thermal-CVD
……

LP-CVD
1

AP-CVD
0.01
500 °C

PE-CVD
1000
mbar AP-CVD
thermal-CVD
100 °C

41
 2. METHODS

PROCESS KINETICS

boundary
layer

layer
substrate

CVD process can be thought of flux of particles

42
 2. METHODS

PROCESS KINETICS: LIKE THERMAL CATALYSIS!

8 Bulk transport
1 Bulk transport
7 Diffusion
2 Diffusion
6 Desorption
4 Decomposition
3 Adsorption 5 Reaction
layer
substrate
CVD process can be thought of flux of particles

8 steps -> which step limits deposition?

1 2 3 4 5 6 7 8
Who is limiting the
flow?
43
 2. METHODS

PROCESS KINETICS
8 Bulk transport
1 Bulk transport
7 Diffusion
2 Diffusion
6 Desorption
3 Adsorption 4 Decomposition
5 Reaction
layer
substrate

CVD process can be thought of flux of particles

8 steps -> which step limits deposition?

1 2 3 4 5 6 7 8
Who is limiting the
flow?
44
 2. METHODS
PROCESS KINETICS
8 Bulk transport
1 Bulk transport
7 Diffusion
2 Diffusion
6 Desorption
3 Adsorption 4 Decomposition
5 Reaction
layer
substrate

JD diffusion flux
D ( cb - cs )
2 Diffusion JD = d
JR surface reaction flux
[J] particles/time

5 Reaction J R = k (cs - ce ) cb concentration in gas flow

cs concentration on surface
ce concentration of end product

δ boundary layer thickness

D diffusion coefficient
k reaction rate constant
45
 2. METHODS

IS STEP 2 (DIFFUSION) OR 5 (REACTION) LIMITING?

( cb - ce ) d
J= (Dd +1) Sh = D
1 = dk
D
k k

• Sherwood number Sh can be used to estimate if CVD reaction is limited by

diffusion or reaction process

• First order reaction assumed

• Limiting cases: Sh >> 1 and Sh <<1

• Also other numbers exist to describe particle fluxes (Reynold number, Thiel
number, Peclet, Nusselt, Damköhler, …)

46
 2. METHODS

KINETIC REGIMES

P = Pressure
T = Temperature

• At very high temperatures, CVD process is limited by diffusion/mass transport

• At low temperatures, CVD process is limited by surface reactions

47
 2. METHODS

SELECTED DEPOSITION METHODS

Methods to Manufacture Thin Films on Substrates

Chemical Vapor Deposition (CVD) Physical Vapor Deposition (PVD) Others

Thermal ALD PECVD Sputtering Evaporation Spin Coating of Sol-Gel

APCVD
Thermal Plasma LPCVD DC AC Magnetron Electroplating Printing

Thermal PLD Electron Beam Screen Printing Inkjet

§ CVD & PVD: deposition of film from gas phase („V“ = vapor)
§ CVD: precursor material is gaseous, chemical reaction on substrate for film growth
§ PVD: precursor material vaporized by physical means, condensation on substrate

48
 2. METHODS
ATOMIC LAYER DEPOSITION (ALD)
Al2O3 Al2O3

silicon wafer

• ALD can be used to deposit ultra-thin conformal layers

• Sub-monolayer growth control
• Variety of materials
Oxides (Al2O3, ZnO, TiO2, SiO2, …)
Nitrides (TiN, SiN, AlN, …)
Metals (Cu, W, Pt, …)

Scott 2010, dx.doi.org/10.1021/nl1030198 |Nano Lett. 2011, 11, 414–418 49

George et al. Chem. Rev. 2010, 110, 111–131
 2. METHODS
ATOMIC LAYER DEPOSITION (ALD)

§ ALD based on chemical reactions (ALD

subclass of CVD)

§ Gases subsequently fed into chamber -

> cycle process and stepwise growth (in
contrast to CVD, where all gases
together)

§ Self-limited reaction between gas &

surface (reaction stops when substrate
completely covered)

E. Kessels, TU Eindhoven 50
 2. METHODS
EXAMPLE: ALD TO DEPOSIT AL 2 O 3

§ Precursors: Al(CH3)3 and H2O

§ Surface covered alternatively by -OH Al donates 3 e-

O needs 2 e-
and -CH3

§ 1 monolayer Al2O3 per cycle

Image courtesy E. Kessels, TU Eindhoven 51

 2. METHODS
EXAMPLE: ALD TO DEPOSIT AL 2 O 3

§ Precursors: Al(CH3)3 and H2O

§ Surface covered alternatively by -OH Al donates 3 e-

O needs 2 e-
and -CH3

§ 1 monolayer Al2O3 per cycle

§ Choose gas dose (pulse) such that

surface reactions saturate

Image courtesy E. Kessels, TU Eindhoven 52

 2. METHODS
ALD SET UP TO DEPOSIT AL 2 O 3

reaction tube with substrate

= TMA
vacuum pump

Wind et al. J. Appl. Phys. 105, 074309 2009 53

 2. METHODS
PLASMA ALD TO DEPOSIT SINGLE ELEMENT FILMS

„M“ = metal or semiconductor

e.g. Ta (from TaCl5), Si (from SiCl2)

• Single element films (metals, semiconductors) very difficult to deposit using

thermal ALD
• Plasma generates hydrogen radicals that help to induce reactions that are not
possible with thermal energy
• Hydrogen radicals reduce metal or semiconductor precursors
George et al. Chem. Rev. 2010, Atomic layer deposition: an overview 110, 111–131 54
 2. METHODS
ALD DEPOSITION TEMPERATURES

• Unwanted processes: condensation, decomposition, incomplete reaction,

desorption
• „ALD window“: nearly ideal ALD behaviour
• Some binary ALD processes don‘t have an ALD window (e.g. TiN with TDMAT, NH3)

George et al. Chem. Rev. 2010, Atomic layer deposition: an overview 110, 111–131 55
 2. METHODS

SUMMARY: VACUUM BASED METHODS

• broad range of possibilities regarding coating of substrates

• can be sorted by phase of the starting material and in physical or chemical

techniques

• choice of method depending on intended layer properties, possible process

conditions during growth and use, desired layer thickness, substrate structure
and properties, desire for upscaling (e.g. lab scale vs industrial application)

• thin films with good quality commonly obtained by several different physical or
chemical vapor deposition methods

56
 3. THIN FILM GROWTH

GROWTH PARAMETERS AND PROPERTIES

Deposition parameters Film properties

- Substrate temperature - Thickness?
- Partial pressures - Composition?
- Particle fluxes - Structure? Chemical
- Plasma parameters binding?
- Substrate conditioning - Defects?
- …

Challenge of thin film technology:

“How do deposition conditions influence film
properties?”
57
 3. THIN FILM GROWTH

PROPERTIES OF THIN FILMS

Film thickness determination of deposition rate
Composition elements, concentrations
Structure binding, crystal structure
Morphology surfaces, columns, nanostructures
Electrical properties photoconductivity, carrier concentration,
carrier lifetime
Optical properties refractive index, luminescence

Mechanical properties adhesion, strain, wear

Magnetic properties

58
 3. THIN FILM GROWTH

DEPOSITION OF THIN FILMS

Adsorption -> Diffusion -> Incorporation -> Nucleation -> Structure development

1 2 3

59
 3. THIN FILM GROWTH

1 FROM ADSORPTION TO INCORPORATION

60
 3. THIN FILM GROWTH

ADSORPTION
The interaction of particles with solid surfaces is known as adsorption. An adsorbed
particle is bound to the surface via a specific binding mechanism.

The competing process to adsorption is desorption.

𝑋 ! +⎕
⇌ 𝑋 "#$
X(g): particle X in gaseous phase
X(ads): particle X adsorbed on surface
⎕: free adsorption site

adsorbent (Adsorbens): the surface material

adsorbate (Adsorbat): species adsorbed on the adsorbent

61
 3. THIN FILM GROWTH

PHYSISORPTION AND CHEMISORPTION

Different interactions can lead to an adsorption of gaseous species on a surface.

These can be classified into:

Physisorption
Species are attracted by the surface through fluctuating polarizations (dipole
interaction): Van-der-Waals interaction
- Attractive forces area weak
- binding energies below 40 kJ/mol (400 meV/particle)

Chemisorption
Strong binding if a covalent binding is formed (chemical bond)
Typical binding energy: a few eV/particle

62
 3. THIN FILM GROWTH

ADSORPTION PROCESS (HERE: DIATOMIC MOLECULE)

Smith: “Thin-film deposition”,

1995

63
 3. THIN FILM GROWTH

SURFACE DIFFUSION
Surface diffusion is crucial for growth of
low-defect films.

Physisorbed particles can move from one

site to another, a potential barrier ES has
to be crossed.

Site with highest binding energy

(chemisorption) can be found.

BUT: kinetic limitations will change these

thermodynamic considerations! Higher
growth rates may lead to less perfect
films

Smith: “Thin-film deposition”, 1995 64

 3. THIN FILM GROWTH

2 FILM NUCLEATION

65
 3. THIN FILM GROWTH

FILM NUCLEATION

a) Layered growth

The total surface energy of the

covered surface is lower than for
the bare one (strong bonding
Smith: “Thin-film
between film and substrate)
deposition”, 1995
Smooth growth

66
 3. THIN FILM GROWTH

FILM NUCLEATION

b) Island growth

If the binding energy is low, a

complete coverage would increase
total surface energy.
Smith: “Thin-film
deposition”, 1995
Minimization of surface energy by
island formation (like water drop)

67
 3. THIN FILM GROWTH

FILM NUCLEATION

c) Mixed growth process

In specific situations growth can

change from layered to island
growth after a few monolayers.
Smith: “Thin-film
deposition”, 1995

68
 3. THIN FILM GROWTH
EXAMPLES OF EPITAXIAL GROWTH
Frank-Van der Merwe

Al2O3 on silicon wafer

Atomic layer deposition scanning electron microscopy

Volmer-Weber model
scanning tunneling microscopy

Pd truncated pyramids on SrTiO3 (nanocrystals) [3]

scanning tunneling microscopy

Electron-beam evaporation

[1] M. Ritala et al, Perfectly Conformal TiN and Al2O3 Films Deposited by Atomic Layer Deposition, 1999 69
[2] F. Silly and M. R. Castell, Phys. Rev. Lett., 2005, 94, 046103, [3] G. Medeiros-Ribeiro et al., Science, 1998, 279, 353–355
 3. THIN FILM GROWTH

FILM NUCLEATION

Example of island growth

Growth of sputtered Ag on silica (SiO2) by RF magnetron sputtering.

Bulir et al., “Preparation of nanostructured ultrathin Ag layer”, J. Nanophoton. 5(1), 051511 (2011)
70
 3. THIN FILM GROWTH

3 STRUCTURE DEVELOPMENT

71
 3. THIN FILM GROWTH

STRUCTURE DEVELOPMENT

- After coalescence of the surface nuclei to a continuous film, the nucleation

step of the thin film is complete
- Development of bulk film structure begins
- Empirical model relates the growth to the relationship between substrate
temperature TS and the melting point of the film TM

72
 3. THIN FILM GROWTH

STRUCTURE DEVELOPMENT

73
 3. THIN FILM GROWTH

STRUCTURE DEVELOPMENT

- Z1 occurs at Ts/Tm is low: surface diffusion is neglegible. The columns

have poor crystallinity, many defects, …
- ZT (transition zone) – similar to Z1 without voids and larger domains
(usually associated with energy enhanced processes)
- Z2 occurs when Ts is high enough that surface diffusion becomes
significant. It consists of tight grain boundaries.
- Z3 with further enhanced temperature (bulk annealing can take place) –
the structure becomes isotropic

The examples are typical for thin film growth, however, they do not appear
in all types of materials

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 3. THIN FILM GROWTH

HZB-laboratory whiskers – application?

STRUCTURE DEVELOPMENT

Smith: “Thin-film
deposition”, 1995

75
 3. THIN FILM GROWTH

STRUCTURE DEVELOPMENT

Further effect of structure development

• Nuclei can be crystalline but do not necessarily have same crystal orientation
® polycrystalline films
• Adsorption of species can depend on the surface structure
® surfaces can grow with different speed, depending on orientation
® “survival of the fittest”
• Island formation can lead to shading effects in directional growth (evaporation,
sputtering)
® a reason for columnar growth and void formation

76
 3. THIN FILM GROWTH

Smith: “Thin-film
INTERFACE FORMATION deposition”, 1995

Interface between film and substrate is not necessarily abrupt. Materials can inter-diffuse or
react with each other. Defects and roughness of substrate can influence the interface.
- Crucial for mechanical stability (adhesion)
- Will determine electrical properties of interface (solar cells!)
- Many industrially relevant substrates (e.g. metal foils) are not very well defined
77
 3. THIN FILM GROWTH

SUMMARY: THIN FILM GROWTH

Deposition may be considered as six sequential substeps, which are determined
both by thermodynamics (materials) AND kinetics (process):

1) Adsorption on the substrate

2) Diffusion over the surface
3) Incorporation: reaction of the adsorbed species with the surface and each other
4) Nucleation: the initial aggregation of the film is called nucleation
5) Structure development: As the film grows thicker it develops a structure or
morphology which includes both roughness and crystallography (amorphous,
fine crystalline, poly-crystalline, mono-crystalline)
6) Sometimes/finally, diffusional interactions occur within the bulk of the film,
with the substrates or within interfaces of multilayers. Often post-treatments
are applied.

78
 4. ADVANTAGES FOR CATALYSIS RESEARCH

APPLICATION TO CATALYSIS: MULTIPLE INTERFACES

Reactants Reactants
Perimeter Reaction interface
Support Sub-surface volume
Inner functional interface Bulk active phase
Bulk active phase Inner functional interface
Sub-surface volume Support
Reaction interface

Image R. Schlögl

• Thin film technologies based on solar cell production allow tailored design with multiple interfaces

• Manipulation of sub-surface chemistry as selectivity-controlling factor

• Can vary structures and compositions of films with few limits

• Support can be charged with additional function (electrical heating, electrical current collector) 79
 4. ADVANTAGES FOR CATALYSIS RESEARCH

THE WORLD’S FIRST GAN BLUE LED

Challenges to overcome:
1. Hetero-epitaxy of GaN to crystallographic (Nobel price in physics 2014, H. Amano, I. Akasaki, S.Nakamura)
perfection
2. p-Type doping of GaN

1) solved by applying a low-temp AlN buffer 2) solved by Mg-doping & annealing

E-beam Thermal
(LEEBI)

H. Amano, Nobel lecture 2014 S. Nakamura, et al. Jpn. J. Appl. Phys. 31, L139 (1992)
 4. ADVANTAGES FOR CATALYSIS RESEARCH

LIQUID PHASE CRYSTALLIZED SILICON

interlayer absorber dopant- & laser device

deposition deposition capping layer crystallization fabrication

CW laser

Si absorber (15 µm)

Interlayer (~280nm)
glass substrate

D. Amkreutz et al. Prog. Photovolt. Res. Appl. 19, 937 (2011)

J. Dore et al., IEEE J-PV 4, 33 (2014) 81
H. Umishio et al. JJAP 57, 021302 (2018)
 4. ADVANTAGES FOR CATALYSIS RESEARCH

INTERFACE ENGINEERING
650

open circuit voltage (mV)

• Barrier stack has to fulfill thermo- 600

mechanical as well as electronic

function 550

65nm
220nm
• PECVD of SiOx/SiNx/SiOxNy , final 500

layer with plasma oxidation

450
ONO ON ON(ON)
• Strong effect of material choice AND
deposition parameters on electronic
properties : Here interfacial carrier
trap density Dit and fixed charge
density QIL,f

82
N. Preissler et al. Prog. Photovolt. Res. Appl. 7, 515 (2017), IEEE J. of Photov. 2018
 5. MOTIVATION

HIGH-EFFICIENCY TANDEM SOLAR CELL MADE @ HZB

Silver (100nm; Thermal evaporation)
Anti-reflective coating (100nm; Thermal evaporation)
IZO (100nm; Sputtering)
SnO2 (20nm; ALD)
C60 (20nm; Thermal evaporation)
Perovskite (400-600nm; Spincoating)
SAM (Self-assembled monolayer; 1nm; Spincoating)
ITO (20nm; Sputtering)
nc-SiOx:H (n) (95nm; PECVD)
a-Si:H (i) (5nm; PECVD)
c-Si (n) (270µm) Al-Ashouri, A., Köhnen, E., et al. (2020). Science
https://doi.org/10.1126/science.abd4016
a-Si:H (i) (5nm; PECVD)
a-Si:H (p) (5nm; PECVD) Mariotti, S., Köhnen, E., et al. (2023). Science
AZO (120nm; Sputtering) https://doi.org/10.1126/science.adf5872
Silver (400nm; Sputtering)

World record solar cells by tailoring material composition and

opto-electronic properties of thin films AND their interfaces 83
5. MOTIVATION

PECVD GROWN NANOCRYSTALLINE SILICON OXIDE

HR-XTEM from a SHJ Single Junction
(n) c-Si
crystals ITO

a-SiOx (n)nc-SiOx:H

(i)a-Si:H
c-Si

Features: Challenges in SHJ cells:

• high transversal & low lateral • Rapid nucleation on a-Si:H
electrical conductivity
• Preserve passivation
• Tunable refractive index ~2… (VOC)
>3

Mazzarella et al., Appl. Phys. Lett. 2015, 106, 023902

 SUMMARY

OVERALL SUMMARY
• Thin film technology allows specifically engineered coatings for certain objects or
conditions with wide range of application
• Choice of deposition method depends on intended layer properties, possible
process conditions during growth and use, desired layer thickness, substrate
structure and properties, potential for upscaling (e.g. lab scale vs industrial
application)
• Deposition conditions influence growth and properties of thin film. The
competition between thermodynamics of the materials and kinetics of the
process can be exploited!
• Thin film technologies allow tailoring of materials and interfaces for catalysis
research and we have very wide open field for exciting science and technology
ahead of us!

85