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Physics of Thin Films

PES 449 / PHYS 549

Introduction and Overview

Ohring: Historical Perspective p. xix

What is a "thin film" ?

thin = less than about one micron ( 10,000 Angstroms, 1000 nm)

film = layer of material on a substrate

(if no substrate, it is a "foil")

Applications:

microelectronics - electrical conductors, electrical barriers, diffusion barriers

magnetic sensors - sense I, B or changes in them

gas sensors, SAW devices

tailored materials - layer very thin films to develop materials with new properties

optics - anti-reflection coatings

corrosion protection

wear resistance

etc.

Special Properties of Thin Films:

different from bulk materials

Thin films may be:

not fully dense

under stress

different defect structures from bulk

quasi - two dimensional (very thin films)

strongly influenced by surface and interface effects

This will change electrical, magnetic, optical, thermal, and mechanical properties.

Typical steps in making thin films:

1. emission of particles from source ( heat, high voltage

2. transport of particles to substrate (free vs. directed)

3. condensation of particles on substrate (how do they condense ?)

.)

Simple model:

on substrate (how do they condense ?) .) Simple model: How do the variables effect film

How do the variables effect film structure and properties ?

What physics is in all this ?

thermodynamics and kinetics

o

phase transition - gas condenses to solid

o

nucleation

o

growth kinetics

o

activated processes

desorption

diffusion

o

allowed processes and allowed phases

solid state physics

o

crystallography

o

defects

o

bonding

electricity and magnetism

o optics

o

o

conductivity - resistivity

magnetic properties

mechanics

o o conductivity - resistivity magnetic properties  mechanics o o stresses in films friction and

o

o

stresses in films

friction and wear

Physics of Thin Films

PES 449 / PHYS 549

Structure of Solids: ideal solids

Ohring: Chapter 1, Section 1.2

Classify solids

crystalline

o atoms show short and long range order

amorphous (non-crystalline)

o atoms show short range order only

We will study crystalline solids first.

Crystal structure

crystals have two parts

1. lattice - regular periodic array of points in space

2. basis - a group of atoms located at each point in the lattice

lattices:

in three dimensions: only 14 unique lattices (Bravais lattices)

examples: (NOTE: the spheres are just points in space - NOT atoms !)

lattice parameter = a o = length of a cube side see Figure 1-1 for

lattice parameter = a o = length of a cube side

see Figure 1-1 for other lattices

basis:

number and arrangement of atoms we put at each lattice point

examples:

Cr

 

o

bcc lattice

o

one Cr atom basis

o

a o = 2.88 Angstroms

Cu

 

o

fcc lattice

o

one Cu atom basis

o

a o = 3.615 Angstroms

Si

 

o

fcc lattice

o

two Si atom basis

 

one Si atom at (0,0,0)

other Si atom at (1/4, 1/4, 1/4)a

 

o

a o = 5.43 Angstroms

Surfaces

For thin films, we are interested in surfaces.

=> cut crystals in different ways.

Describe surfaces by Miller indices.

General Procedure Specific Example
General Procedure
Specific Example

1. Cut crystal along some

plane.

cut along a face of a cube

cut along a face of a cube

2. Determine x, y, z, intercepts

(x o , y o , z o )

(1, infinity, infinity)

3. Take reciprocals and reduce

to smallest integer.

3. Take reciprocals and reduce to smallest integer.

(100) plane

[if we had used the (200) plane, reduce to (100)]

See Figure 1-3 for other examples.

Other cubic surfaces:

plane, reduce to (100)] See Figure 1-3 for other examples. Other cubic surfaces: What would these

What would these surfaces look like ?

Note how open some surfaces are packed and how dense others are packed. Different surfaces

Note how open some surfaces are packed and how dense others are packed.

Different surfaces have different arrangements of atoms => different properties.

[crystal models demonstration]

Close packed planes:

Two surfaces produce the maximum possible density for packing spheres. The surface layers and second layers of atoms are identical, but the positions of atoms in the third planes are different.

hcp (0001) = base plane of the hexagonal close packed structure

o ABABAB repeat pattern

fcc (111) = diagonal cut through the face centered cubic sructure (shown above)

o ABCABCABC repeat pattern

[see handout figures]

Crystal Directions

define a vector [h k l] between two lattice points

when the direction is negative, instead of a minus sign, use a bar over the number.

instead of a minus sign, use a bar over the number. angle (  ) between

angle () between any two vectors [h 1 k 1 l 1 ] and [h 2 k 2 l 2 ] :

[h 1 k 1 l 1 ] and [h 2 k 2 l 2 ] :

for cubic lattices:

[h k l] is normal vector to (h k l) plane

spacing (d) between (hkl) planes is given by:

l) plane  spacing (d) between (hkl) planes is given by: where a o is the

where a o is the length of one side of the cube face

example: spacing between (100) planes in a simple cubic lattice:

: spacing between (100) planes in a simple cubic lattice: Non-crytalline (amorphous) solids glasses not stable

Non-crytalline (amorphous) solids

glasses

not stable state for most pure metals

can be formed by very rapid cooling (10 6 K/sec)

readily formed from many metal alloys, semiconductors, oxides - especially at low temperatures

generally less dense than crystalline materials

no crystalline defects since no crystal structure

Physics of Thin Films

PES 449 / PHYS 549

Structure of Solids: defects in solids

Ohring: Chapter 1, Section 1.3

Classification of Defects in Crystalline solids

polycrystalline solid - contains several crystalline regions which are randomly oriented

several crystalline regions which are randomly oriented Most crystalline materials have many defects. Some (like

Most crystalline materials have many defects.

Some (like Silicon) can be grown with relatively few defects.

Three types of defects:

1. Planar defects - grain boundaries interfaces between two single crystal regions of different orientation

atoms at grain boundaries tend to be loosely bound => more reactive (corrosion) and accelerated

atoms at grain boundaries tend to be loosely bound

=> more reactive (corrosion) and accelerated diffusion along grain boundaries

typical grain sizes: 0.01 m - 100 m (micron)

How many atoms in a solid are at grain boundaries ?

rough model:

many atoms in a solid are at grain boundaries ? rough model: assume grains are all

assume grains are all cubes with sides of length l

l = grain size

a = atomic lattice parameter

n = number of atoms in one row of the grain

then, l = na

n = number of atoms in one row of the grain then, l = na What

What would be the result for spherical grains of diameter, l ?

A somewhat better argument using truncated octahedra leads to the fraction being about 3.35 (a/l). (See Christian "Theory of Transformations in Metals and Alloys", p. 332).

example:

for l = 0.1 micron (1000 Angstroms) and a = 3 Angstroms

about 10 atoms out of 1000 are at grain boundaries (1 %)

Number of grain boundaries in film (grain size) depends on deposition rate and substrate temperature.

generally:

lower T => smaller grains => many boundaries

hight T => larger grains => fewer boundaries

grain size is often proportional to film thicknes

(thinner films tend to have smaller grains)

2. line defects - dislocations

example: edge dislocation - from inserting an extra row of atoms

distorts lattice => stresses (compression and tension)

edge dislocation - from inserting an extra row of atoms distorts lattice => stresses (compression and

very common: often 10 10 - 10 12 dislocations/ cm 2 in films

form from:

 

film growth process

dislocations in substrate continuing into film

contamination on substrate

3. point defects

self interstitial - extra atom

vacancy - missing atom

substitutional impurity - impurity atom in lattice

interstitial impurity - impurity atom not in regular lattice site

impurity - impurity atom not in regular lattice site in principle you can eliminate all of

in principle you can eliminate all of these except vacancies

vacancies arise from thermodynamics (entropy)

vacancies vacancies arise from thermodynamics (entropy) fraction of vacancies (f) o where k B = Boltzmann's

fraction of vacancies (f)

o

from thermodynamics (entropy) fraction of vacancies (f) o where k B = Boltzmann's constant = 1.381

where k B = Boltzmann's constant = 1.381 x 10 -23 J/K

typically E f is about 1 eV

at room temperature, f is about 10 -17

point defects often arise from

fast deposition

low substrate temperatures

=> no time for atoms to move to crystal lattice sites

Surface Roughness

films always have some statitistical distribution of thickness across the film

some statitistical distribution of thickness across the film in the worst case: generally observed less roughness

in the worst case:

distribution of thickness across the film in the worst case: generally observed less roughness Physics of

generally observed less roughness

Physics of Thin Films

PES 449 / PHYS 549

Structure of Solids: Bonds and electrons in solids

Ohring: Chapter 1, Section 1.4

Bonding in materials:

bonds lower the total energy of a system of atoms => solids are more stable than free atoms

bonds from electrostatic and quantum attraction and repulsion

electron structures around ion cores lead to different bond types and strengths

four basic types of bonds:

metallic

o

relatively weak bond (1 -2 eV)

o

complicated mixture of electrostatic and quantum attraction and repulsion

o

no direction to bonds

=> easy to deform

o

examples: most metals, Fe, Ni, Cr

ionic

o

strong bonds (2 -10 eV)

o

Coulomb attraction of oppositely charged ions

o

Coulomb and quantum repulsions

o

no direction to bonds

o

examples: NaCl, MgF 2 , ZnS

covalent

o

strong bonds (2- 10 eV)

o

"sharing" of electrons

o

bonds are directional

=> hard to deform

o

examples: Si, Ge, GaAs

Van der Waals

o

weak bonds (around 0.2 eV)

o

often neglected

o

from distortion of electron clouds

o

examples: inert gasses, organics

Bonds: attractive and repulsive components

all bonds have attractive and repulsive components

components all bonds have attractive and repulsive components exact details of repulsive and attractive parts give:

exact details of repulsive and attractive parts give:

lattice parameters

binding energy

elastic modulus (from shape of well)

Surface bonds

surface atoms are less tightly bound than bulk atoms

bonds surface atoms are less tightly bound than bulk atoms Electrons in Solids Metals : some

Electrons in Solids

Metals:

some electrons bound to ion cores

other electrons are "free electrons" => conduction

electrons are "free electrons" => conduction  = work function = energy needed for electron to

= work function = energy needed for electron to escape from metal

(important in thermionic emission, photoemission)

Insulators:

large gap between filled and empty states

=> electrons have no where to go => very poor conductors

electrons have no where to go => very poor conductors Semiconductors: similar to insulators except gap

Semiconductors:

similar to insulators except gap is smaller (around 1 eV)

=> can apply voltage or heat to excite electrons into conduction band

doped semiconductors create states in the gap => easier to excite electrons across gap

Physics of Thin Films

PES 449 / PHYS 549

Thermodynamics and Phase Diagrams

Ohring: Chapter 1, Section 1.5

Thermodynamics

tells us what can happen - - - not how fast it will happen

free energy change

G = G final - G initial = H - T S

where H = enthalpy change, T = temperature, S = entropy change

G < 0 => process is allowed

G > 0 => process is forbidden

G = 0 => equilibrium

nature will minimize free energy

Chemical Reactions

aA + bB <=> cC

We can relate the free energy change for this reaction to the activity, a, (kind of concentration).

It can be shown:

the activity, a, (kind of concentration). It can be shown: where R = gas constant =

where R = gas constant = 1.987 cal/(mole K)

note if a i > a i(eq) you have supersaturation

often G is about the same as G o which is the free energy change in standard state

example: Ellingham diagrams

oxide formation

if Al and Al 2 O 3 are in contact with Si and SiO 2

if Al and Al 2 O 3 are in contact with Si and SiO 2 :

Al will be oxidized to Al 2 O 3

SiO 2 will be reduced to Si

No information about rate.

if you have a Ni-Al alloy

Al oxidizes preferentially => may end up with Al 2 O 3 film on top

=> may end up with Al 2 O 3 film on top another example is stainless

another example is stainless steel (Cr, Fe, Ni) which forms a Cr + Fe oxide layer

Phase Diagrams

arise from minimizing free energies for each phase

use for

gas - liquid - solid transitions

structural changes (graphite <--> diamond)

stable alloys

ONE COMPONENT SYSTEM

example: Carbon

example: Carbon the two phases (diamond and graphite) can coexist on the line that separates them

the two phases (diamond and graphite) can coexist on the line that separates them

example: Iron

can coexist on the line that separates them example: Iron triple point has three phases coexisting

triple point has three phases coexisting (very well defined point)

TWO COMPONENT SYSTEMS

examples: alloys such as GaAs, NiCr, WSi

variables: P, T, and composition => 3 dimensional diagrams

typically we fix the pressure at one atmosphere

draw diagrams of Temperature vs. composition

Examine several common types of two component phase diagrams:

Binary Solid Solutions:

completely soluble in liquid and solid state at all compositions

phases and compositions: at I: liquid with composition C o (about 30% Si, 70% Ge)

phases and compositions:

at I: liquid with composition C o (about 30% Si, 70% Ge)

at II: liquid with composition C o and solid with composition C S (II)

at III: liquid with composition C l (III) and solid with composition C S (III)

at IV: solid with composition C o

How much (mole fraction) is in each phase ?

at III:

C o How much (mole fraction) is in each phase ? at III: examples of other

examples of other systems with binary solid solution phase diagrams:

Cu-Ni, Pt-Rh, NiO-MgO, FeO-MgO

components have same crystal structure

Binary Eutectic diagrams:

limited solubility in the solid state

two solid phases:   fcc substitutional solid of Sn in Pb  tetragonal substitutional

two solid phases: 

fcc substitutional solid of Sn in Pb

tetragonal substitutional solid of Pb in Sn

(note the reduced melting points of the alloys from either Pb or Sn)

phases and compositions:

at I: liquid of composition C o (about 35% Sn and 65% Pb)

at II: liquid of composition C o and solid of composition C (II) and no solid

at III: liquid of composition C l (III) and solid of composition C (III) and no solid

at IV: solid of composition C (IV) and solid of composition C (IV)

How much of each phase:

same rule as above for binary solid solutions

examples of other systems having binary eutectic phase diagrams:

Bi-Cd, Al-Si, CaO-MgO

These phase diagrams are equilibrium phase diagrams.

Thin Films are generally NOT equilibrium growth processes.

(usually T is too low or deposition rate is too high.)

=> we can form other structures

Remember these examples have been at atmospheric pressure.

phase diagram does change at other pressures (like inside a vacuum system)

[HANDOUT: Si-Ge phase diagrams at other presssures]

Physics of Thin Films

PES 449 / PHYS 549

Kinetics and Diffusion

Ohring: Chapter 1, Sections 1.6, 8.1 - 8.2

Kinetics

= how fast it will happen

we will concentrate on mass transport

= atoms diffusing through a solid

Diffusion in one dimension - Fick's 1st and 2nd Laws

Fick's 1st Law = "stuff moves from where you have lots to where you have little"

Now let us consider the flux of atoms into and out of a particular volume
Now let us consider the flux of atoms into and out of a particular volume

Now let us consider the flux of atoms into and out of a particular volume in the solid.

The fluxes (J) may be different at different positions (x) in the material.

Mathematically:

at different positions (x) in the material. Mathematically: rate of increase of matter in the region
at different positions (x) in the material. Mathematically: rate of increase of matter in the region

rate of increase of matter in the region = rate of flow in - rate of flow out

= (J 1 - J 2 ) x = - Jx

or this is also = rate of change of concentration in the volume

so

Solve this equation as a boundary value problem (see example in Ohring p. 34-36. Atomic

Solve this equation as a boundary value problem (see example in Ohring p. 34-36.

Atomic view

for simplicity consider a cubic lattice

34-36. Atomic view for simplicity consider a cubic lattice There is always a potential energy barrier

There is always a potential energy barrier to diffusion (activation energy).

What do we expect mathematically for the flux to the right (from position1 to 2):

do we expect mathematically for the flux to the right (from position1 to 2): Similarly we

Similarly we can find the flux to the left:

(note: if we had used the gas constant, R, instead of Boltzmann constant, k, then

(note: if we had used the gas constant, R, instead of Boltzmann constant, k, then the energy would be the diffusion energy/mole)

COMMENTS:

diffusion increases with temperature

Diffusion Coefficients

self diffusion (element A in A): D A

vacancy diffusion: D V

chemical diffusion (element A in B): D AB

grain boundary diffusion: D gb

surface diffusion: D s

actually D is typically NOT CONSTANT, D is a function of:

o

position

jump frequency depends on local atomic arrangement and defects

temperature gradients

o

direction in lattice

o

time

defects, concentrations, temperature may vary with time

high diffusivity paths:

grain boundaries

three dimensional dislocation networks

surfaces

These are all more open structures with higher jump frequencies and lower energy barriers.

o D o and E D are different for these paths

Usually the cross sectional areas of these are small compared to the rest of the film.

In general (but not necessarily at high temperature): D S > D gb > D

Arrhenius Plot

for determining activation energies

start with Fick's First Law:

activation energies start with Fick's First Law: Other effects on diffusion Diffusion can be changed by
activation energies start with Fick's First Law: Other effects on diffusion Diffusion can be changed by

Other effects on diffusion

Diffusion can be changed by stress fields, electric fields, other energy gradients (interfaces)

[note: Ohring changes notation here: uses diffusion free energy per mole G D instead of diffusion energy per atom E D so all of the k's become R's.]

Examine what happens when we apply a field:

How fast do atoms diffuse?

How fast do atoms diffuse? Physics of Thin Films PES 449 / PHYS 549 Nucleation and

Physics of Thin Films

PES 449 / PHYS 549

Nucleation and Growth

Ohring: Chapter 1, Section 1.7

Connection to Phase Diagrams

Can phase diagrams help us in understanding rates ?

Consider cooling a liquid into a solid through a eutectic point:

Can phase diagrams help us in understanding rates ? Consider cooling a liquid into a solid

at point A: solid is not stable so will not form

at point B: solid and liquid are both stable so no driving force to solid

at point C: liquid is unstable - will form solid

at point D: liquid is unstable - will form solid

o further from equilibrium => greater driving force to form solid

Transformation to solid phase

Requires:

1.

Nucleation of new phase

2.

growth of new phase

Nucleation:

depends on:

liquid phase instability

o

driving force toward equilibrium (as above)

o

increases as we move to lower temperatures

diffusion of atoms into clusters

o increases at higher temperatures

combine these two terms (multiplication) to determine the total nucleation rate

(multiplication) to determine the total nucleation rate The maximum rate of nucleation is at some T

The maximum rate of nucleation is at some T < T e

Growth:

growth of the phase is diffusion controlled => increases with temperature

Transformation rate:

total rate of forming solid is product of nucleation rate and growth rate

Nucleation details When moving into a 2 phase region on phase diagram - how does

Nucleation details

When moving into a 2 phase region on phase diagram - how does the new phase form ?

Two issues:

1. Thermodynamics: Is nucleation possible ? (energy minimization)

2. Kinetics: How fast does it happen ? (nucleation rate)

Homogeneous Nucleation

vapor --> liquid (solid) for a pure material with NO substrate

--> liquid (solid) for a pure material with NO substrate Energy minimization involves two terms: 1.

Energy minimization involves two terms:

1. volume transition

2. surface formation

volume transition:

where  is the atomic volume, P S is the pressure above the liquid (solid),

where is the atomic volume, P S is the pressure above the liquid (solid), and P V is the pressure in the vapor.

We want P V > P S so that G is negative

=> supersaturation provides the driving force.

surface formation:

provides the driving force. surface formation: Change in surface energy is always positive when forming

Change in surface energy is always positive when forming surfaces.

Total energy change:

force. surface formation: Change in surface energy is always positive when forming surfaces. Total energy change:
force. surface formation: Change in surface energy is always positive when forming surfaces. Total energy change:

note:

initial formation of nuclei has increase in G => metastable

if r < r* then nuclei shrink to lower G

if r > r* then nuclei grow to lower G

r* is a critical radius for nuclei

grow to lower G  r* is a critical radius for nuclei Films will also have

Films will also have an interface term => heterogeneous nucleation (coming soon!)

Nucleation rate

How fast will the critical nucleus continue to grow ?

Consider the rate at which atoms will join the critical nuclei:

the rate at which atoms will join the critical nuclei: expect nucleation rate to be given

expect nucleation rate to be given by

the critical nuclei: expect nucleation rate to be given by N* = concentration of critical nuclei

N* = concentration of critical nuclei (nuclei/cm 3 )

A* = critical surface area of nuclei

= flux of atom impingement (atoms / cm 2 sec)

Consider each of these three terms:

Physics of Thin Films PES 449 / PHYS 549 Film Formation I Ohring: Chapter 5,

Physics of Thin Films

PES 449 / PHYS 549

Film Formation I

Ohring: Chapter 5, sections 1 - 3

Competing Processes

adding to film:

o impingement (deposition) on surface

removing from film:

o

reflection of impinging atoms

o

desorption (evaporation) from surface

We can characterize the process of getting atoms onto a surface with

o

sticking coefficient = mass deposited / mass impinging

Steps in Film Formation

1. thermal accommodation

2. binding

3. surface diffusion

4. nucleation

5. island growth

6. coalescence

7. continued growth

We will examine each of these steps in turn.

1. Thermal accommodation

impinging atoms must lose enough energy thermally to stay on surface

assume that E = kT so we can talk about energy or temperature equivalently

= kT so we can talk about energy or temperature equivalently thermal accommodation coefficient ( 

thermal accommodation coefficient (T )

equivalently thermal accommodation coefficient (  T ) Examine energy transfer to lattice: one dimensional model

Examine energy transfer to lattice:

one dimensional model from B.McCarrol and G. Ehrlich, J. Chem. Phys. 38, 523 (1963).

consider a chain of atoms connected by springs:

if rebound is strong enough - atom escapes if not - atom is trapped -

if rebound is strong enough - atom escapes

if not - atom is trapped - oscillates and loses energy to lattice

RESULTS:

atom is trapped if E v < 25 E desorb

o

E desorb is typically 1-4 eV

o

trapped if E v < 25 - 100 eV

o

equivalently T v < 2500 - 10,000 K

o

most deposition processes have E v < 10 eV

o

MOST ATOMS ARE TRAPPED

thermal accommodation is very fast

o around 10 -14 seconds

2. Binding

two broad types of surface bonds:

physisorption (physical adsorption)

o

Van der Waals type

o

weak bonds

o

0.01 eV

chemisorption (chemical adsorption)

o

chemical bonds

o

strong bonds

o

1 - 10 eV

Can we keep the atoms on the surface ?

competition between impinging atoms (deposition) and desorption of atoms

deposition: determined by deposition rate (atoms/cm 2 sec) =

desorption: determined by

rate (atoms/cm 2 sec) = desorption : determined by  � G d e s =

G des = free energy of desorption

T S = temperature of substrate

= frequency of adsorbed atom attempting to desorb = lattice vibration frequency

atom attempting to desorb = lattice vibration frequency Consequences:  heat up substrate => lower coverage

Consequences:

heat up substrate => lower coverage

stop depositing => lower coverage until not film

o films are not stable !!!

What is wrong with this model ?

missing surface diffusion

3. Surface diffusion

allows clusters of adsorbed atoms to form

clusters are stable => film forms

How far do they diffuse ?

from random walk analysis [see F. Reif "Fundamentals of Statistical and Thermal Physics" p.

486]

diffusion distance (X) is given by

Consider two cases:

"Fundamentals of Statistical and Thermal Physics" p. 486] diffusion distance (X) is given by Consider two
4. Nucleation How do clusters form ? => nucleation Two competing processes in cluster formation

4. Nucleation

How do clusters form ? => nucleation

Two competing processes in cluster formation

clusters have a condensation energy per unit volume (G V ) which lowers the desorption rate (higher barrier)

clusters have a higher surface energy than individual atoms

o clusters want to break up to minimize energy

Capillarity Model (= heterogeneous nucleation)

nucleation on a substrate

assume nuclei are spherical caps

as with homogeneous nucleation, we can plot � G against r and determine a critical

as with homogeneous nucleation, we can plot G against r and determine a critical nucleus size:

as with homogeneous nucleation, we can plot � G against r and determine a critical nucleus

How do nuclei grow initially ?

How do nuclei grow initially ? Substrates are NOT flat steps, kinks, etc. have higher E

Substrates are NOT flat

steps, kinks, etc. have higher E des barrier => longer residence time on surface

=> preferred sites for nucleation

time on surface => preferred sites for nucleation Nucleation Rate How quickly do nuclei form ?

Nucleation Rate

How quickly do nuclei form ?

(similar analysis to homogeneous nucleation rate from earlier)

Combining all these expressions:

Combining all these expressions:

Combining all these expressions:

Capillarity Model - applications

What can we learn from the capillarity model about effects of deposition rate and substrate temperature on nucleation ?

from before:

rate and substrate temperature on nucleation ? from before: To see how the lab variable (deposition

To see how the lab variable (deposition rate, substrate temperature) change the basic physics examine the derivatives (and plug in some typical values):

examine the derivatives (and plug in some typical values): Summary: high T and/or low deposition rate

Summary:

high T and/or low deposition rate => large crystal grains

low T and/or high depostion rate => small polycrystalline structure

Problem: Can we apply macroscopic thermodynamics to nuclei of 2-100 atoms ?

Atomistic (Statistical) Nucleation Model

Walton - Rhodin Theory

treat clustes of atoms like molecules rather than solid caps

consider the bonds between atoms

similar to capillarity model, but now include E i* = energy to break apart a critical cluster of i* atoms into individual atoms.

other terms:

N i* = concentration of critical clusters per unit area

N 1 = concentration of single atoms per unit area

n o = total density of adsorption sites on surface

 n o = total density of adsorption sites on surface advantages of this model: 

advantages of this model:

depends on microscopic parameters

includes crystalographic information

o since bonds between atoms are included

critical size (i*) depends on substrate temperature

o

model shows transitions in growth modes

o

preferred i* increases with T

[Section 5.3.2 has other film growth models]

Physics of Thin Films

PES 449 / PHYS 549

Film Formation II

Ohring: Chapter 5, sections 4-6

5. Island Growth

observe 3 growth modes experimentally

1. Island growth (Volmer - Weber)

form three dimensional islands

source:

o

film atoms more strongly bound to each other than to substrate

o

and/or slow diffusion

each other than to substrate o and/or slow diffusion 2. Layer by layer growth (Frank -

2. Layer by layer growth (Frank - van der Merwe)

generally highest crystalline quality

source:

o

film atoms more strongly bound to substrate than to each other

o

and/or fast diffusion

quality  source: o film atoms more strongly bound to substrate than to each other o

3. Mixed growth (Stranski - Krastanov)

initially layer by layer

then forms three dimensional islands

=> change in energetics

three dimensional islands  => change in energetics When would we expect to see each of

When would we expect to see each of these ?

in energetics When would we expect to see each of these ? The layer growth condition
in energetics When would we expect to see each of these ? The layer growth condition

The layer growth condition with cosine greater than 1 looks odd. This is the case where the angle theta is undefined because for layer growth there really is no point where the substrate, vapor and film come together and therefore, no way to define the angle.

6. Island Coalescence

three common mechanisms:

1.

Ostwald ripening

atoms leave small islands more readily than large islands

more convex curvature => higher activity => more atoms escape

curvature => higher activity => more atoms escape 2. Sintering  reduction of surface energy 3.

2. Sintering

reduction of surface energy

atoms escape 2. Sintering  reduction of surface energy 3. Cluster migration  small clusters (<100

3. Cluster migration

small clusters (<100 Å across) move randomly

some absorbed by larger clusters (increasing radius and height)

absorbed by larger clusters (increasing radius and height) 7. Thick films - zone models Further growth

7. Thick films - zone models

Further growth depends on:

bulk diffusion

surface diffusion

desorption

geometry:

o shadowing (line of sight impingement)

 geometry: o shadowing (line of sight impingement)  Relative importance of these processes depends on

Relative importance of these processes depends on

substrate temperature (T)

deposition rate (

on  substrate temperature (T)  deposition rate ( ) Plot these variables to find regions

)

Plot these variables to find regions with similar film structure (similar properties)

regions with similar film structure (similar properties) See handout in class (from J. A. Thornton, J.

See handout in class (from J. A. Thornton, J. Vac. Sci. Technol. 12 (July/Aug 1975))

Zone

Temperature

Diffusion

Other Processes

Structure

 

T

< 0.2 - 0.3

   

small grains, many

1

limited

 

T

 

.

voids

 

M

 
       

mixed small and large grains, fewer voids

T

< 0.2 - 0.5

T

surface

renucleation during growth

 

T

 
 

M

   
 
 

T

< 0.3 - 0.7

     

2

surface

grain boundary migration

columnar grains

 

T

 
 

M

     
   

bulk

grain boundary migration; recrystallization within grains

large grains

3

T > 0.5 T M

(dominates) +

(sometimes

surface

columnar)

more info: see article by Grovenor, Acta Metall. 32, 773 (1984) and book by Machlin

Columnar structures

o

very common

o

from limited atomic mobility

o

often oriented slightly toward source

mobility o often oriented slightly toward source Films are typically lower density than bulk o more

Films are typically lower density than bulk

o more porosity at macro, micro and nano scales.

Grain size dependence on deposition rate and substrate temperature

o grain size typically increases with increasing film thickness, increasing substrate temperature, increasing annealing temperature, and decreaseing deposition rate.

annealing temperature, and decreaseing deposition rate. Other factors affecting film growth 1. Substrate  not

Other factors affecting film growth

1. Substrate

not really a featureless plane

atomic structure => epitaxy

o relationship of film crystal structure to substrate crystal structure

defects

2. Contamination

from:

o nucleation sites

poor background pressure

impure deposition source

dirty substrate

changes the energies (surface energies, desorption energy, surface diffusion energy)

energies, desorption energy, surface diffusion energy) 3. Impinging particle energy 0.5 eV ------------------->

3. Impinging particle energy

0.5 eV -------------------> 10 - 20 eV --------> 100-1000 eV

thermal evaporation ----- sputtering --------- accelerated (bias)

interactions of incident particles with film/substrate produce:

sputter removal of surface atoms

insertion of particles into film or substrate

increased local temperature

defects

shock (pressure) waves

Physics of Thin Films

PES 449 / PHYS 549

Plasma Physics

references:

"Classical Electromagnetic Radiation" M. A. Heald and J. B. Marion

"Foundations of Electromagnetic Theory" J. R. Reitz, F. J. Milford and R. W. Christy

"Electromagnetic Fields and Waves" P. Lorrain, D. R. Corson, and R. Lorrain

Plasmas

Plasma:

dilute ionized gas

(often at high temperature)

contains free electrons (light) and positive ions (heavy)

excellent conductor with current mainly carried by electrons

Usually we concentrate on the behavior of the electrons because they are more mobile.

Creating a plasma:

If we start with a gas of neutral atoms, we create a plasma by removing an electron from an atom, leaving a positive ion.

Typical ionization energies are shown in the table:

Element

First Ionization Potential

Second Ionization Potential

Argon

15.7 eV

27.76 eV

Mercury

10.3

.

Neon

21.4

.

Oxygen

13.6

34.93

Sodium

5.1

47.0

Chromium

6.7

16.6

Since 1 eV corresponds to about 11,600 K, it is typically not practical to achieve ionization by thermal processes. Instead we rely on electron collisions with atoms.

electrons ionize by collision most effectively for energies around 100 eV

we rely on electron collisions with atoms. electrons ionize by collision most effectively for energies around
 

number of ions formed per cm of travel in 10 mTorr gas for electrons with about 100 eV

element

He

0.015

Ne

0.025

H

2

0.040

N

2

0.100

Ar

0.110

Hg

0.210

electron collisions can also produce excited (but not ionized) atoms,

collisions between excited atoms and ground state atoms can lead to ionization of the ground state atom (Penning ionization)

characterizing a plasma:

characterize by temperature (energy), electron density (N e ) and particle density or neutral atom density (N)

cold plasma

o

o

particle energy of a few eV

typical of most thin film processes

hot plasma

a few eV typical of most thin film processes  hot plasma o o particle energy

o

o

particle energy of a few thousand eV

typical of nuclear fusion and some astrophysics

electron temperature often > ion temperature

o especially in dilute plasmas

density

o

at pressure of 5 mTorr: total particle density about 10 13 particles/cm 3

o

weakly ionized: ion density = electron density is about 10 8 ions/cm 3

o

strongly ionized: ion density = electron density is about 10 12 ions/cm 3

These parameters are often grouped as follows:

Debye length

o

distance over which significant charge separation can occur

o

D (cm) = 743 (T e / N e ) 1/2

with density in electrons / cm 3

plasma frequency

o

o

to be derived shortly

p = 56,548.67 N e

1/2

with density in electrons / cm 3

critical degree of ionization

o

o

if N e / N is much greater than this critical degree of ionization, the plasma behaves as though it is fully ionized

c = 1.73 x 10 12 eA T e

2

where eA is the electron-atom collision cross section in cm 2 (typically 10 -16 - 10 -15 )

Electrostatics

charged particles in a constant Electric field (E) with no magnetic field (B = 0)

When subjected to Electric field:

o

charges redistribute themselves to shield the interior from the fields

o

plasma region is field free and approximately neutral

o

for T = 2000 K and N = 10 18 electrons/meter 3 , sheath thickness is about 1 micrometer

3 , sheath thickness is about 1 micrometer  electrons in a constant Magnetic Field (

electrons in a constant Magnetic Field (B) with no electric field (E=0)

o

thickness is about 1 micrometer  electrons in a constant Magnetic Field ( B ) with
frequency of gyration =  c y c l o t r o n =

frequency of gyration = cyclotron = qB / m

note: electrons have a longer actual path length before reaching one side of the system => more likely to ionize a neutral gas atom.

electrons in a uniform, constant E and B with E perpendicular to B

o motion has three components

1. constant velocity v parallel in direction of B

2. gyration about the B field lines

3. constant drift velocity v d = E/B perpendicular to E and B

note v d does not depend on mass or charge - so all particles drift together

depend on mass or charge - so all particles drift together Electrodynamics apply an oscillator model

Electrodynamics

apply an oscillator model to electrons in the plasma

at low frequencies (<50 kHz) ions and electrons both oscillate

at high frequencies (>50 kHz) heavy ions can not follow switching fields => only electrons oscillate while ions are relatively stationary

Examine forces on electrons:

driving force from varying E field

no restoring force since electrons are not bound (spring constant = 0)

o not true if charge separation in plasma leads to electrostatic restoring forces

damping term, , from collisions (this could be large)

o = collision frequency

consider effects of electromagnetic wave on plasma (with no static fields)

from F = ma we can write down an equation of motion:

fields) from F = ma we can write down an equation of motion: Special case: Dilute

Special case: Dilute Plasmas

dilute => few collisions so is small (<< 

same approximations as before

for  p (evanescent domain) k is imaginary => waves are attenuated When is a

for  p (evanescent domain)

k is imaginary => waves are attenuated

When is a plasma dilute ?

criteria: 

to put numbers in, let us say 

estimate collision frequency from kinetic theory of gasses:

estimate collision frequency from kinetic theory of gasses: � d 2 =  e A =

d 2 = eA = electron - atom collision cross section

using typical values

d = 1 Å = 1 x 10 -10 m

m = 9.1 x 10 -31 kg

T = 10 eV = 116,000 K

then = 6.65 x 10 -14 N (where N is in particles/m 3 )

if the incident frequency, , is 1000 Hz

o then we want < 10 Hz which means N < 1.5 x 10 14 atoms/m 3 (or 1.5 x

10 8 atoms/cm 3 or 4 x 10 -9 torr)

if the incident frequency is 1,000,000 Hz

o then we want < 10,000 Hz which means N < 1.5 x 10 17 atoms/m 3 (or 5 x

10 11 atoms/cm 3 or 4 x 10 -6 torr)

Reality check: 1 torr = 3.5 x 10 22 atoms/m 3 are NOT dilute

so most plasmas in our processes

Another reality check: is the plasma frequency for these conditions greater than the incident frequency ?

Using N = 1.5 x 10 17 atoms/m 3 (and assuming f = 0.1 and q = 1.6x 10 -19 C), plasma frequency = 7 x 10 9 Hz which is much greater than anything else.

Special Case: Dense Plasmas

collisions between charged particles are common electrons and ions are in thermal equilibrium

electrons and ions move together

equilibrium theory formulation of plasmas

particles maintain a Maxwell-Boltzmann velocity distribution

kinetic properties and transport properties of particles can be calculated from this.

Applications of plasmas

cleaning / etching of surfaces

sputter deposition source

bombardment during deposition to modify film

activation of reactive gasses

Plasma Sources

plate electrodes

o

low plasma densities (10 9 - 10 10 charged particles per cm 3 )

o

common in sputter deposition

o

discuss further during sputter deposition

Inductively coupled plasma (ICP)

o

high plasma densities (10 11 - 10 12 charged particles per cm 3 )

o

operates well at lower gas densities (< 50 mTorr)

o

can be used up to atmospheric pressures (and beyond)

o

couple RF energy inductively into plasma (lossy electrical conductor)

produces more efficient ionization

Helicon

o

high plasma densities (10 11 - 10 12 charged particles per cm 3 )

o

operates well at lower gas densities (< 50 mTorr)

o

radiates RF energy into plasma for resonant absorption

produces more efficient ionization

Electron cyclotron resonance (ECR)

o

high plasma densities (10 12 - 10 13 charged particles per cm 3 )

o

operates well at lower gas densities (down to 0.1 mTorr)

o

couples microwave energy to electrons by matching frequency to electron gyration frequency

c = eB /

m e

produces more efficient ionization

o

control the plasma density with microwave power and gas pressure

o

can also control ion species created (O 2 + , O + )

density with microwave power and gas pressure o can also control ion species created (O 2

Physics of Thin Films

PES 449 / PHYS 549

Kinetic Theory of Gasses

Ohring: Chapter 2, sections 1, 2

Pressure and Vacuum

Many thin film processes involve vacuum.

"vacuum" = lower molecular density than in our atmosphere

results in a lower pressure of gas - so typically measure this

MANY different units are commonly used. Torr microns mbar Pascals (N/m 2 ) atmospheres (mm
MANY different units are commonly used.
Torr
microns
mbar
Pascals
(N/m 2 )
atmospheres
(mm
psi
(lb/in 2 )
dyne/cm 2
(µm Hg)
molecules
/ m 3
Hg)
1
mbar =
1
100
9.87x10 -4
0.75
750
0.0145
1000 2.65x10 22
1.45x10 -
1
Pa =
0.01
1
9.87x10 -6
7.5x10 -3
7.5
10 2.65x10 20
4
1
atm =
1010
10,100
1
760 7.6x10 5
14.69
1.01x10 6
2.69x10 25
1
Torr =
1.333
133.3
1.31x10 -3
1 1000
0.0193
1333
3.53x10 22
1.33x10 -
1.93x10 -
1
µm =
0.133
1.31x10 -6
0.001
1
5 1.333
3.53x10 19
3
1
psi =
68.94
6.89x10 3
0.068
51.71
5.17x10 4
1 6.89x10 4
1.83x10 24
1
dyne/cm 2
7.50x10 -
1.45x10 -
0.001
0.10 9.87x10 -7
4 0.75
1 2.65x10 19
5
=
1
3.77x10 -
3.77x10 -
2.83x10 -
2.83x10 -
5.47x10 -
3.77x10 -
molecule/m 3
3.72x10 -26
23
21
23
20 25
20 1
=

Pressure Conversion Calculator

enter exponents as "e-7" for example: 5.3x10 -7 should be entered 5.3e-7

-- still has some trouble displaying very small or very large numbers -- Pressure Conversion
-- still has some trouble displaying very small or very large numbers --
Pressure Conversion Calculator
mbar Pascals
atmospheres
Torr
microns
psi
dyne/cm 2
molecules/m 3

Composition of gas in vacuum chamber is very different from atmosphere

pumps remove certain gasses preferentially

Component

Volume % in dry air

Volume % in ion pumped chamber at 2x10 -9 torr

N 2

78

%

trace

O 2

21

%

trace

Ar

0.93

%

trace

CO 2

0.03

%

3

%

CH 4

trace

3

%

H

2 O

trace

5

%

CO

trace

6

%

H

2

trace

78 %

Ideal Gas Law

much of vacuum technology can be understood from the ideal gas law

more correctly: the equation of state of an ideal gas

PV = NkT

where

P = absolute pressure

V = volume

N = number of gas molecules

k = Boltzmann's constant

T = gas temperature (in K)

Kinetic Theory of Gasses - Gas Flow

Assumptions:

Gasses are composed of a very large number of very small particles.

o "very small" => very small compared to the distance between particles

Particles are always moving rapidly in a straight line.

Particles exert no forces except during collisions.

Freeze other molecules and examine motion of one molecule:

Freeze other molecules and examine motion of one molecule: What is the distribution of velocities ?

What is the distribution of velocities ?

determine most properties from this

Maxwell velocity distribution

higher T: shifts curve to right; broadens and lowers it lighter mass: shifts curve to

higher T: shifts curve to right; broadens and lowers it

lighter mass: shifts curve to right; broadens and lowers it

See Figure 2-1 in Ohring.

How fast are the molecules moving ?

Figure 2-1 in Ohring. How fast are the molecules moving ? k = Boltzmann's constant T

k

= Boltzmann's constant

T

= temperature of the gas (K)

m = mass of the molecule

Not surprising:

The hotter it is, the faster they move.

The lighter they are, the faster they move.

At room temperature:

Molecule

v

rms (m/sec)

v

rms (miles/hour)

H

2

 

1700

 

3790

N

2

 

450

 

1000

Ar

 

380

 

850

How far does a molecule travel before it collides with another molecule ?

a molecule travel before it collides with another molecule ?  = mean free path d

= mean free path

d

= diameter of a molecule

n

= number per unit volume

For air at room temperature, the mean free path can be expressed as:

at room temperature, the mean free path can be expressed as: P = pressure in torr

P = pressure in torr

will be in cm.

Pressure

Mean Free Path

1 atm

6.7 x 10 -6 cm

1 torr

5 x 10 -3 cm

1 millitorr

5 cm

10

-6 torr

50 m

10

-9 torr

50 km

Gas Flow:

three regimes:

viscous flow

o mean free path << size of the system (D)

o

gas - gas collisions dominate

o

molecules "drag" one another along in the flow

o

when D(cm) P (Torr) > 0.5

for air at room temperature

intermediate (transition) flow

o

mean free path comparable to size of system (D)

o

complicated flow

molecular flow

o

mean free path >> size of system

o

gas - wall collisions dominate

o

molecules move independently of one another

o

when D(cm) P (Torr) < 0.005

for air at room temperature

This information is summarized in Ohring Figure 2-3.

Kinetic Theory of Gasses - Interactions with surface

How many gas molecules collide with a surface each second ?

= 0.25 n v rms

= collision rate of gas molecules

n

= number of molecules per unit volume

v

rms = average velocity of a gas molecule

In terms of things we can directly measure:

a gas molecule In terms of things we can directly measure:  will be in molecules/

will be in molecules/ cm 2 - sec

P

is the pressure in torr

M

is the molecular weight of the gas molecule

T

is the temperature in K

For example:

Nitrogen (N 2 ) has a molecular weight M = 28. If we have a chamber with nitrogen at room temperature (293 K) and a pressure of 1 x 10 -7 torr:

= 3.88 x 10 13 molecules/cm 2 - sec

How long does it take to form a single complete layer of gas on a surface ?

take to form a single complete layer of gas on a surface ? t m =

t m = time to form a monolayer (in seconds)

n

= number of molecules per unit volume

v

rms = average velocity of the molecules

d

= diameter of a molecule

For air at room temperature, we can express this as:

t m = 1.86 x 10 -6 / P

where P is the pressure in torr.

pressure

t

m

1 atm

2 x 10 -9 sec

10

-6 torr

2 seconds

10

-9 torr

31 minutes

Vapor Pressure

in equilibrium, a certain pressure ot atoms (vapor pressure) will exist above solid surfaces

Do not make high vacuum chambers out of Zinc. If you heat it to 200

Do not make high vacuum chambers out of Zinc. If you heat it to 200 C (476 K) the vapor pressure of Zn is 6 x 10 -6 torr.

Physics of Thin Films

PES 449 / PHYS 549

Evaporation

Ohring: Chapter 3, sections 1 - 4

Physical Vapor Deposition

Evaporation

Sputter Deposition

Process:

1. source material -> gaseous state

3.

deposit atoms on substrate

Evaporation

Overview:

3. deposit atoms on substrate Evaporation Overview: 1. Atoms to gas state  heat source until

1. Atoms to gas state

heat source until P vapor > 10 -4 torr

some sources sublime from solid, others evaporate from liquid

compounds may break apart

o

produce films with different stoichiometry

o

SiO 2 --> SiO 2-x

metal alloy sources do not give same alloy in film

o

components evaporate independently based on each separate vapor pressure

o

could try to adjust source composition

o

BUT composition of alloy source changes with time

describe evaporation rate (flux) from kinetic theory

o o where
o
o
where

P vap = vapor pressure (Torr)

M = molecular weight

cm 2 => area of source

can convert this to mass flux

o o at P vap = 10 -2 torr, mass flux = 10 -4 grams/cm
o
o
at P vap = 10 -2 torr, mass flux = 10 -4 grams/cm 2 sec

2. Transport to surface

line of sight deposition

want to avoid collisions in gas

o

long mean free path

o

good vacuum

o

let h = source to substrate distance

for h of 10 - 100 cm, want P < 10 -5 torr

bigger h => lower P

Particles have energies comparable to evaporation temperature

o 1000 C is about 0.2 eV

distribution of evaporant

o

depends on geometry of source

o

consider 2 geometries

Point Source

source o consider 2 geometries  Point Source    = tilt of dA S

= tilt of dA S from radial direction

projection of dA S onto sphere of radius r = dA S cos

dM S = mass hitting dA S

M e = total evaporated mass

mass hitting dA S  M e = total evaporated mass   distribution depends on

distribution depends on r and

Surface Source

hitting dA S  M e = total evaporated mass   distribution depends on r

For many materials, this is equivalent to Knudsen cell

 For many materials, this is equivalent to Knudsen cell if directions are random, only dA

if directions are random, only dA S cos/ 4r 2 are headed in right direction

integrate over time and source

right direction    integrate over time and source now distribution depends on horizontal position

now distribution depends on horizontal position as well

Experimentally observe

position as well  Experimentally observe   greater n => more directed evaporation 3. Deposition

greater n => more directed evaporation

3. Deposition onto substrate

Consider film thickness and purity

THICKNESS

since dM/dA s depends on r, , so does film thickness (d)

consider flat substrate, perpendicular to source

for this geometry:  cos  = h/r , r = (h 2 + l

for this geometry:  cos= h/r , r = (h 2 + l 2 ) 1/2

in general:

 = h/r , r = (h 2 + l 2 ) 1 / 2 in

point source:

r = (h 2 + l 2 ) 1 / 2 in general: point source: surface

surface source:

l 2 ) 1 / 2 in general: point source: surface source: surface source has slightly

surface source has slightly poorer thickness uniformity

better uniformity:

decrease sample size (l)

inrease distance to substrate (h)

o

need bigger chamber

o

need better vacuum

o

wastes evaporant

use multiple sources

move substrate during deposition

use rotating amsk to reduce evaporant near center

o

 use multiple sources  move substrate during deposition  use rotating amsk to reduce evaporant

put source and substrate on same sphere surface

o o o No dependence on or r !!! o planetary fixtures
o
o
o
No dependence on or r !!!
o
planetary fixtures

FILM PURITY

PROBLEM: contamination from source materials

o SOLUTION: use pure materials (99.99999%)

PROBLEM: contamination from source or substrate heaters

o SOLUTION: use materials with low diffusion

see tables of crucibles for each material

on line tables:

PROBLEM: residual gas in chamber

o

o

o

gives two "sources" impinging

evaporant:

o o o gives two "sources" impinging  evaporant:  residual gas: impurity concentration in film:

residual gas:

impinging  evaporant:  residual gas: impurity concentration in film:   P in Torr; M

impurity concentration in film:

 residual gas: impurity concentration in film:   P in Torr; M g and M

P in Torr; M g and M e are molecular weights

SOLUTION:

better vacuum

higher deposition rate

note: P and T g are not independent

Physics of Thin Films

PES 449 / PHYS 549

Sputter Deposition

Ohring: Chapter 3, sections 5 - 6

Overview

Deposition Ohring: Chapter 3, sections 5 - 6 Overview 1. Atoms into gas state at target:

1. Atoms into gas state

at target:

target atoms ejected

target ions ejected (1 - 2 %)

electrons emitted

o helps keep plasma going

Ar + ions reflected as Ar neutrals

Ar buried in target

photons emitted

We are most interested in the first of these: target atoms going into the gas phase

Sputtering process

o

in the first of these: target atoms going into the gas phase Sputtering process o 

momentum transfer process

o

involves top 10 Å

o

model as hard sphere collisions

good for energies < 50 keV

95 % of incident energy goes into target

 

o

=> COOL the target

5 % of incident energy is carried off by target atoms

 

o

typical energies of 5-100 eV

target atoms come off with a non-uniform distribution

 

o

more atoms normal to the surface

o

cosine distribution (like surface source)

 

characterize process by sputter yield (S)

S

= number ejected / number incident

S

depends on

target material

 

o

binding energy

o

mass of atoms

sputtering gas

 

o

mass of atoms (S increases for heavier gasses)

o

incident energy (S increases for higher energies)

geometry

 

o

most efficient 20-30 degrees from glancing

 
 

for normal incidence sputtering:

o

geometry   o most efficient 20-30 degrees from glancing    for normal incidence sputtering: o

maximum around 10 kV

sputtering threshold

S is about 1-10 typically

For calculating S we need:

number of atoms ejected

o

depends on momentum and energy transferred

these depend on relative masses and collision angle

maximum energy transferred to target atom in hard sphere collision

o

transferred to target atom in hard sphere collision o  depends on binding energy of target

depends on binding energy of target atom

number of layers involved in process

o mean free path of ion in target

typically about 2 layers

surface density of target atoms

collision cross section of ion with target atom

Sputtering alloy targets

composition of alloy in film is approximately the same as alloy in target (unlike evaporation)

Why ?

rapid mixing in liquids (evaporation)

slow diffusion mixing in solids (sputtering)

o

target reaches steady state

o

surface composition balances sputter yield

Process:

Initial alloy of A and B

If S A > S B , remove more A

o enriches surface in B

More B on surface => more B sputtered

surface composition reaches steady state

o

surface enriched in B

o

bulk composition sputtered

o

f A S A / C A = f B S B / C B

ABABABABABABAB

BAB. B. BA. B . AB ABABBABABBAB

where f = surface fraction and C = bulk composition

alloy targets need to be conditioned by sputtering a few hundred Å before depositing

2. Transport to substrate

Target atoms pass through Ar gas and plasma environment

o

one Ar + ion for every 10,000 Ar neutrals

o

electrons in plasma collide with Ar neutrals to form ions and more electrons

Target atoms collide with Ar atoms, Ar + ions and electrons

o

treat as random walk "diffusion" through gas

o

target atoms lose energy (down to 1-10 eV)

o

chemical reactions may occur in gas

o

not a line of sight process (unless pressure reduced)

can coat around corners

3. Deposit on substrate

target atoms and ions impinge

electrons impinge

Ar atoms impinge

o

Ar pressure about 0.1 torr

o

Ar may be incorporated into film

energetic particles may modify growth

substrates heat up

o

100 - 200 C is common

o

for a thermally isolated sample (no heat conduction)

for a thermally isolated sample (no heat conduction)     = substrate density (g/cm
for a thermally isolated sample (no heat conduction)     = substrate density (g/cm

= substrate density (g/cm 3 )

c = substrate heat capacity (J/gC)

d = substrate thickness (cm)

= film atomic volume (cm 3 /atom)

D-DOT = deposition rate (Å/min)

t = time (secs)

energies are in eV/atom

note: the constant does have units

Physics of Thin Films

PES 449 / PHYS 549

Sputter Deposition Techniques

Ohring: Chapter 3, section 7

Basic Techniques

DC (diode)

RF (radio frequency)

magnetron

DC sputtering