MSE 550

Presentation #2

What is a thin film? Science background overview of film growth crystal structure and defects (dislocations, grain boundaries) diffusion properties of vacuum Film formation Thermal accommodation Sticking and surface diffusion nucleation of film growth modes (island, layer by layer, mixed) coalescence of film continued growth (zone models) other factors energetic deposition amorphous films epitaxial growth Deposition parameters and techniques (relate the knobs on equipment to what happens on the film) Evaporation Vacuum Arc Deposition Sputter Deposition DC RF Chemical Vapor Deposition Ion Beam assisted deposition plasma enhanced deposition (PECVD, ECR . . .

How are thin films made? What are the basic parts of deposition systems?
source transport region substrate - deposition region temperature deposition rate deposition energy

What parameters can we control?

Within the framework established above, examine each of the following deposition methods in detail:
evaporation cathodic arc vaporization sputter deposition
DC RF

Molecular Beam Epitaxy Chemical Vapor Deposition Ion Beam assisted deposition / ion implantation plasma enhanced deposition (PECVD, ECR . . . ) Spin coating Electroplating

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

 Typical steps in making thin films: emission of particles from source ( heat, high voltage . . .) transport of particles to substrate (free vs. directed) condensation of particles on substrate (how do they condense ?)

Simple model:

 Mechanisms? thermodynamics and kinetics

phase transition - gas condenses to solid nucleation growth kinetics activated processes
desorption diffusion

allowed processes and allowed phases

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

nd 2

Ficks law

 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):

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

Examine what happens when we apply a field:

How fast do atoms diffuse?

Nucleation and Growth

Connection to Phase Diagrams Can phase diagrams help us in understanding rates ? Consider cooling a liquid into a solid through a eutectic point:

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 further from equilibrium => greater driving force to form solid

Nucleation
depends on: liquid phase instability
driving force toward equilibrium (as above) increases as we move to lower temperatures

diffusion of atoms into clusters

increases at higher temperatures

combine these two terms (multiplication) to determine the total nucleation rate The maximum rate of nucleation is at some T < Te

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 the new phase form ? Two issues: Thermodynamics: Is nucleation possible ? (energy minimization) Kinetics: How fast does it happen ? (nucleation rate) Homogeneous Nucleation vapor --> liquid (solid) for a pure material with NO substrate

 Energy minimization involves two terms: volume transition surface formation volume transition:

where W is the atomic volume, PS is the pressure above the liquid (solid), and PV is the pressure in the vapor. We want PV > PS so that G is negative => supersaturation provides the driving 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

 Nucleation rate How fast will the critical nucleus continue to grow ? Consider the rate at which atoms will join the critical nuclei:
expect nucleation rate to be given by

N* = concentration of critical nuclei (nuclei/cm3) A* = critical surface area of nuclei [ = flux of atom impingement (atoms / cm2sec) Consider each of these three terms:

Film Formation I Competing Processes adding to film:

impingement (deposition) on surface reflection of impinging atoms desorption (evaporation) from surface sticking coefficient = mass deposited / mass impinging

removing from film: We can characterize the process of getting atoms onto a surface with

Steps in Film Formation thermal accommodation binding surface diffusion nucleation island growth coalescence 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

thermal accommodation coefficient (ET)

if rebound is strong enough - atom escapes if not - atom is trapped - oscillates and loses energy to lattice RESULTS: atom is trapped if Ev < 25 Edesorb Edesorb is typically 1-4 eV trapped if Ev < 25 - 100 eV equivalently Tv < 2500 - 10,000 K most deposition processes have Ev < 10 eV MOST ATOMS ARE TRAPPED thermal accommodation is very fast around 10-14 seconds

2. Binding two broad types of surface bonds: physisorption (physical adsorption)

Van der Waals type weak bonds 0.01 eV

chemisorption (chemical adsorption)

chemical bonds strong bonds 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/cm2sec) = desorption: determined by (Gdes = free energy of desorption TS = temperature of substrate no = frequency of adsorbed atom attempting to desorb = lattice vibration frequency

Consequences: heat up substrate => lower coverage stop depositing => lower coverage until not film 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:

4. Nucleation How do clusters form ? => nucleation Two competing processes in cluster formation clusters have a condensation energy per unit volume ((GV) which lowers the desorption rate (higher barrier) clusters have a higher surface energy than individual atoms
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 nucleus size:

How do nuclei grow initially ?

Substrates are NOT flat steps, kinks, etc. have higher Edes barrier => longer residence time on surface => preferred sites for nucleation

Nucleation Rate How quickly do nuclei form ?

Nucleation Rate

 Nucleation Rate

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

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

 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 clusters of atoms like molecules rather than solid caps consider the bonds between atoms similar to capillarity model, but now include Ei* = energy to break apart a critical cluster of i* atoms into individual atoms. other terms: Ni* = concentration of critical clusters per unit area N1 = concentration of single atoms per unit area no = total density of adsorption sites on surface

advantages of this model: depends on microscopic parameters includes crystallographic information since bonds between atoms are included critical size (i*) depends on substrate temperature model shows transitions in growth modes preferred i* increases with T

Film Formation II 5. Island Growth observe 3 growth modes experimentally 1. Island growth (Volmer - Weber) form three dimensional islands source:
film atoms more strongly bound to each other than to substrate and/or slow diffusion

 2. Layer by layer growth (Frank - van der Merwe) generally highest crystalline quality source:
film atoms more strongly bound to substrate than to each other and/or fast diffusion

3. Mixed growth (Stranski - Krastanov) initially layer by layer then forms three dimensional islands => change in energetics

 When would we expect to see each of these ?

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

2. Sintering reduction of surface energy

 3. Cluster migration small clusters (<100 across) move randomly some absorbed by larger clusters (increasing radius and height)

7. Thick films - zone models Further growth depends on: bulk diffusion surface diffusion desorption geometry:
shadowing (line of sight impingement)

yRelative importance of these processes depends on ysubstrate temperature (T) ydeposition rate

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

Zone Temperature 1 T 2 T < 0.2 - 0.3 TM T < 0.2 - 0.5 TM T < 0.3 - 0.7 TM T > 0.5 TM

Diffusion limited surface surface

Other Processes . renucleation during growth grain boundary migration

Structure small grains, many voids mixed small and large grains, fewer voids columnar grains large grains (sometimes columnar)

grain boundary bulk migration; (dominates) + recrystallization within surface grains

 Columnar structures
very common from limited atomic mobility

often oriented slightly toward source

Films are typically lower density than bulk more porosity at macro, micro and nano scales. Grain size dependence on deposition rate and substrate temperature grain size typically increases with increasing film thickness, increasing substrate temperature, increasing annealing temperature, and decreasing deposition rate.

Other factors affecting film growth 1. Substrate not really a featureless plane atomic structure => epitaxy
relationship of film crystal structure to substrate crystal structure nucleation sites

defects 2. Contamination from: poor background pressure impure deposition source dirty substrate changes the energies (surface energies, desorption energy, surface diffusion energy)

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