S.M.

Shivaprasad
ICMS/CPMU, JNCASR
In this talk:

•Beauty is skin deep!

•X-ray Photoelectron Spectroscopy
•Scanning Tunneling Microscopy
•Some of our work using these
 Dangling bonds

(2x1)

(1x1)
Catalysis and Chemical Reactions : Petroleum and Chemicals
Corrosion and segregation: Oil, gas pipe lines, Buildings, vehicles, strucutres
Semiconductor Interfaces: Microelectronics and future devices
Thermionic Emission: Desplay devices, TV tubes, PDP, LCD
Paints and Coatings: Optical, wear & protection, electrical, magnetic
Brittle Fracture: Turbo machines, bridges, machines
Nanostructures: All applications, smart drugs, genetic engg.,
Crystal Growth: Semiconductors, Optical, Magnetic
Contaminants: Medicine, Food, semiconductors
Interfaces: Solar cells, night vision, tooth and bone implants
 Surface Science and Nano-science
Semiconductor nanoparticles Self assembly by heteroepitaxy

Surface atoms - Reduced Co-ordination

Nanophase - Most are surface atoms !

3D 2D-sheet 1D- wire 0D-dot

Density of states: Where electrons can stay !

 CdSe nanoparticles
1- 10 nm size

Atom Molecule Solid

Conduction Band

Band Gap

Valence Band

Size Band Gap

 Dangling bonds

Confinement: Particle in a box

Nano-phase atoms - All surface atoms !

n=4
Surface to volume ratio
n=3 Surface to Volume Ratio

60
n=2
% of surface atoms
50
40
30
20
n=1 10
0
0 20 40 60 80 100 120
Discrete energy levels No of atoms/cluster

Quantization
 Need for Ultra high vacuum
Study surfaces:
Surface sensitive probes

Deg. of Vacuum (Pressure) Mean Free Path Time / ML

(Torr) (m) (s)
Atmospheric 760 7 x 10-8 10-9
Low 1 5 x 10-5 10-6
Medium 10-3 5 x 10-2 10-3
High 10-6 50 1
UltraHigh 10-10 5 x 105 104
Electrons as probes: Small size, charge and large scattering
 11
Base Pressure: 3x10-11 Torr

XPS (Perkin Elmer: 1257) AES (Varian VT 112)

Techniques:
1. Auger Electron Spectroscopy
2. Low Energy Electron Diffraction
3. X-ray Photoelectron Spectroscopy
4. Energy Loss Spectroscopy
XPS, AES, UPS, EXAFS, LEED, LEEM, SHG, SIMS, PES, ELS,
HREELS, ISS, LEIS, MEIS, SEXAFS, STM, AFM, MFM…...
 Aspects of Heteroepitaxial Growth
Hetero: Different
Epi: Upon
Taxy: Ordered

Aspects of Heteroepitaxial Growth:

• Lattice Mismatch Ni/Ru(001)
• Surface Free Energy Pt/W(111)
• Dangling bond M/Si(111), (100)

Nanostructures: Controlled sizes, assembly

 Heteroepitaxial Growth (Interface Formation):
Arrival
Re-evap.
1/a =  exp(-Ea/kT)

Thermodynamics
vs.
Step Special Diffu. Binding Inter-diffu Kinetics

Growth Modes:

Frank van der Merwe

Wolmer Weber
(layer)
(island)

Stranski-Krastanov
(layers + island)
Is/Iso = (1-x) exp(-nl/) + x exp[-(n+1)l/] 0x1
Ideally terminated Si surface Surfaces

Dangling bonds
A new approach to the formation of compatible
substrates for GaN growth
 Advantages of Solid State Lighting
technology

• Highly efficient light sources

• Substantial reduction in electrical energy
consumption
• Substantial improvements in human visual
experience (True white light)
• Cheaper and long lasting, no sudden break-
downs
• Creation of III-V semiconductor technologies
Solid State Lighting : Prospects and progress

Efficiency of White LEDs

120
100
80

Lumens per watt

60
40
20
0
-201985 1990 1995 2000 2005 2010 2015
Year

Uses of LED:
1. Mobile 40%
2. Signs 23%
3. Automotive 18%
4. Others (biological) 12%
5. Illumination 5%
6. Signals 2%
InGaN based Photovoltaics:
Efficiency of > 70% - Achievable 50%
Involves deposition of multi-layers:

Standard LED design

Saphire (Al2O3) and GaN
•Lattice Parameter Mismatch (13%)
•Thermal Expansion Mismatch (33%)

GaN on SiC and GaAs

 High Defect Density > 1010 /cm3

Cree Demonstrates 131 Lumens per Watt White

LED
DURHAM, NC, JUNE 20, 2007 — Cree, Inc. (Nasdaq:
CREE), a market leader in LED solid-state lighting components, today
announced LED efficacy test results that set a new benchmark for the LED
industry. Cree reported results of 131 lumens per watt white LED efficacy,
confirmed by the National Institute of Standards and Technology in
Gaithersburg, Maryland. Tests were performed using prototype white LEDs
with Cree EZBright™ LED chips operating at 20 mA and a correlated color
temperature of 6027 K.

“This is the highest level of efficacy that has been publicly reported for a white
GaN buffer layers
LED and raises the bar for the LED industry,” said Scott Schwab, Cree general
manager, LED chips. “This result once again demonstrates Cree’s leadership in
LED technology and provides a glimpse into the future as to why we believe
LED-based lighting products could not only save energy, but also change the
way people use light.”

“Technical advancements at the component level are critical to growing the

emerging white LED lighting space. Cree’s results speak to the exciting
developments underway that will enable new white light applications and
subsequently facilitate market adoption,” stated Fritz Morgan, chief technology
officer for Color Kinetics, a leading innovator of LED lighting systems and
technologies.

Lumens-per-watt is the standard used by the lighting industry to measure the

conversion of electrical energy to light. As a reference, conventional
incandescent light bulbs are typically in the 10 to 20 lumens per watt range,
while compact fluorescent lamps range from 50 to 60 lumens per watt.
 Outstanding limits:

• Green emission (Indium incorporation)

• Si wafer technology adaptation (SiC epitaxial
layer)
• Defect density- types of defects (70 arc.sec
assymetric XRD)
• Band dispersion and surface/interface
modifications
• Substrate Thermal Conductivity
 Outstanding Issues in Growth of LED:
30 lum/watt to 500 lum/watt (Theor. 763 lum/watt)

1. Problems in p-type doping (Si doping – lattice expansion)

2. H-ions from ammonia detrimental

3. Substrate compatibility (lattice mismatch): Sapphire, SiC, AlN, Si

6. Substrate Thermal Conductivity:

4. Defect density (lateral epitaxial growth): Reduction of Schowbel barrier

5. Dislocation density: Effects on Quantum Efficiency and Life time

6. Layer Thickness Control : Layer uniformity

7. Thin metal contacts: Al, Ti and Au alloys: Schottky contacts

8. Interface sharpness and integrity: avoiding interfacial phases

 Need for Ultra high vacuum
Study surfaces:
Surface sensitive probes

Deg. of Vacuum (Pressure) Mean Free Path Time / ML

(Torr) (m) (s)
Atmospheric 760 7 x 10-8 10-9
Low 1 5 x 10-5 10-6
Medium 10-3 5 x 10-2 10-3
High 10-6 50 1
UltraHigh 10-10 5 x 105 104
 NEED FOR ULTRA-HIGH VACUUM
From Kinetic Theory of Gases:
Molecular Flux:
Z = Nc/4V Hertz-Knudsen equation

N/V =Mol per unit vol, c is av. Speed of molecules

For a gas of Mol Wt M at temp T

c = √(8RT / m) R=gas const.,

Since PV= nRT and N=nNA,

Z=nNAP √(8RT / m) or Z=NAP / √(2MRT)

For Pressure in Pa (Nm-2) and M (g mol-1)

Z= 2.635 x 1024 P / √(MT) collisions m-2 s-1

Calculating of effective pumping speed
P1: pressure at the inlet of the pipe
S1: pumping speed at the inlet of
pipe
C: conductance of the pipes
P2: pressure at the inlet of the pump
S2: pumping speed at the inlet of
the pump
Continuum of gas throughput
Q = P1S1 = P2S2
Q = C(P1-P2) C: conductance of the
pipe
P2 = P1C/(S2 +C)
S1 = S2 C/(S2 +C)
If C >> S2 S1=S2
If C = S2 S1=1/2S2
Pumping Equation
 Obtaining UHV
Roughing UHV

Sorption Sputter Ion

Turbo_Rotary Diffusion
Diaphragm Cryopump
Titanium Sublimation
 VACUUM PUMPING METHODS
VACUUM PUMPS
(METHODS)

Gas Transfer Entrapment

Vacuum Pump Vacuum Pump

Positive Displacement Kinetic Adsorption

Vacuum Pump Vacuum Pump Pump

Reciprocating Rotary Drag Fluid Entrainment Ion Transfer Cold Trap

Displacement Pump Pump Pump Pump Pump

Diaphragm Liquid Ring Gaseous Ejector Bulk Getter Getter

Pump Pump Ring Pump Pump Pump Pump

Piston Rotary Turbine Liquid Jet Diffusion Getter Ion Sublimation

Pump Piston Pump Pump Pump Pump Pump Pump

Multiple Vane Sliding Vane Axial Flow Gas Jet Diffusion Self Purifying Evaporation
Rotary Pump Rotary Pump Pump Pump Ejector Pump Diffusion Pump Ion Pump

Rotary Radial Flow Vapor Jet Fractionating Sputter Ion

Plunger Pump Pump Pump Diffusion Pump Pump

Dry Roots Molecular

Cryopump
Pump Pump Drag Pump

Turbomolecular
Condenser
Pump
Rotary Vane, Oil-Sealed Mechanical Pump

Pump Mechanism How the Pump Works

Sorption Pump

Vapour
Pressure
Oil Diffusion Pump
LN2 reservoir with baffles
Approximate Vapor
Gas Pressure (mbar)

Water (H2O) 10-22

Argon (A) 500
Carbon Dioxide (CO2) 10 -7
Carbon Monoxide (CO) >760
Helium (He) >760
Hydrogen (H2) >760
Oxygen (O2) 350
>760
Neon (Ne)
760
Nitrogen (N2)
<10 -10
Solvents
 DP Pumping Speed

1 2 3 4
Pumping Speed (Air)

Critical Point

1. Compression Ratio Limit

2. Constant Speed
3. Constant Q (Overload)
4. Mechanical Pump Effect

10-10 10--3 10--1

Inlet Pressure (Torr)
 Turbomolecular Pump
INLET FLANGE ROTOR BODY

STATOR BLADES
HIGH PUMPING SPEED

HIGH COMPRESSION

BEARING
EXHAUST

HIGH FREQ. MOTOR

BEARING

Rotor - stator assembly

Sputter Ion Pumps:
Cryo Pumps:
Measuring UHV:

Penning
Ion Gauge
Bayer-Alpert Gauge (Nude)
Spinning Rotor Gauge
Gauges
Gauge Operating Ranges
Ultra High
High Vacuum Rough Vacuum
Vacuum
Bourdon Gauge
Capacitance Manometer
Thermocouple Gauge
Pirani Gauge
Hot Fil. Ion Gauge
Cold Cathode Gauge
Residual Gas Analyzer
McLeod Gauge
Spinning Rotor Gauge

10-12 10-10 10-8 10-6 10-4 10-2 1 10+2

P (mbar)
 Thermocouple Gauge

How the gauge works

Ionization gauges
Problems that appear to be Leaks

Permeation
Diffusion
Real
Leaks
Outgassing Virtual
Backstreaming
 Residual Gas Analyzer

QUADRUPOLE
HEAD

CONTROL UNIT
How the RGA works
 RGA SPECTRUM
RELATIVE INTENSITY NORMAL (UNBAKED)
H2 O SYSTEM
(A)
H2 N2,, CO
CO2

MASS NUMBER (A.M.U.)

RELATIVE INTENSITY

N2
SYSTEM WITH
AIR LEAK
H2 O
(B)
O2
H2 CO2

MASS NUMBER (A.M.U.)

UHV Materials:

Degassing properties
Machinability
Bakability
Permeability
Transfer mechanisms (Bellows)
THANK YOU
Effective Pumping Speed
•If we attach a 500 L/s pump to a chamber with a 500 L/s conductance port, what is the effective pumping speed (EPS) from the chamber. Before calculating, let us set some
limits intuitively: A 500L/s pump is connected to the chamber by some magical 'infinite' conductance port, would the pump's pumping speed be affected?
Answer - No. EPS is 500 L/s
•Two 500L/s pumps are connected to the same chamber by separate, 'infinite' conductance ports, what is the EPS?
Answer - EPS is 1000 L/sec.
•A 500L/s pump is connected to the chamber by a 500L/sec port, would the EPS be higher or lower than 500L/sec?
Answer - Lower.
•This indicates that adding pumping speed and conductance in series lowers the overall pumping speed, while adding them in parallel increases the pumping speed. This
sounds identical to the series/parallel connections of electrical capacitances. Indeed, pumping speeds (PS) and conductances (C) are added to give effective pumping speed
(EPS) using exactly the same mathematic form as capacitances. To calculate series connection of chamber and pump noted above:
•1/EPS = 1/PS + 1/C
•Substituting the numbers from our initial example, we find 1/EPS = 1/500 + 1/500
1/EPS = 2/500
1/EPS = 1/250
•EPS = 250 liter per sec That is, when the pumping speed and conductance are of equal value, the effective pumping speed is half the quoted pumping speed. Newcomers to
vacuum technology, and even some old-timers, are surprised by this number.

  Adding other components only worsens the problem. For example, what if we put an LN2 trap with 500L/sec conductance between the port and pump?
•1/EPS = 1/500 + 1/500 + 1/500
1/EPS = 3/500
1/EPS = 1/167
•EPS = 167 liter per sec
•Clearly, using the quoted PS as the effective PS will cause serious errors in estimating base pressure and pump down time.

  Now, we will take the ridiculous situation and connect a 2000L/sec pump to a chamber by a tube with 10L/sec conductance and calculate the EPS. 1/EPS = 1/2000 + 1/10
1/EPS = 201/2000
1/EPS = 1/9.95
•EPS = <10 liter per sec
Conclusions
One critical fact should be extracted from this segment. The effective pumping speed never exceeds the value of the minimum conductance (or pumping speed) of the
individual parts that are stacked together. Expressed differently, if one component in the stack has a 10L/sec conductance, the effective pumping speed cannot exceed 10L/sec
even if a 2,000,000L/sec pump is attached to it! (Remember - vacuum doesn't suck!
Assignment 1:

Plot the relationship between gas pressure (x-axis), time for surface
contamination and mean free path lengths for He, H2, N2 and Ar,
assuming ideal gas and sticking coefficient of 1.