Process steps for Field Emitter devices built on

Silicon wafers
And 3D Photovoltaics on Silicon wafers

David W. Stollberg, Ph.D., P.E.

Research Engineer and Adjunct Faculty

GTRI_B-1
Field Emitters

GTRI_B-2
Doped Si

GTRI_B-3
 •Deposit SiO2 (~10mm)

•Variable for Height

SiO2

Doped Si

GTRI_B-4
 •Deposit gate

•(poly Si or Cr, ~200nm)

poly-Si
SiO2

Doped Si

GTRI_B-5
 ••Doped
SiO2 Si

•poly-Si

plan view Spincoat Photoresist

poly-Si
SiO2

Doped Si

elevation view

GTRI_B-6
 ••Doped
SiO2 Si •Pattern

•Develop

•poly-Si

plan view
Resist

poly-Si
SiO2

Doped Si

elevation view

GTRI_B-7
 •Etch gate and insulator

isotropically
••Doped
SiO2 Si

•poly-Si

plan view
Resist
poly-Si
SiO2

Doped Si

elevation view

GTRI_B-8
 •Deposit catalyst metal

•Fe shown

•Ni possible with barrier layers

••Doped
SiO2 Si

•poly-Si

plan view Fe catalyst

Resist
poly-Si
SiO2

Doped Si

elevation view

GTRI_B-9
 ••Doped
SiO2 Si

Lift off & Dice

poly-Si

plan view

poly-Si
SiO2

Doped Si

elevation view

GTRI_B-10
 ••Doped
SiO2 Si

poly-Si •Grow CNTs

plan view

poly-Si
SiO2

Doped Si

elevation view

GTRI_B-11
 •Connect and test @ HPEPL

•Langmuir Probe

••Doped
SiO2 Si

poly-Si

plan view
e- e- e-

poly-Si
SiO2 V

Doped Si Measure I, V

elevation view

GTRI_B-12
GTRI_B-13
CNT growth parameter
for CNTs ≤ 2µm
CVD growth:
•N2 and NH3 flowed at 100sccm and
160scmm
•Temperature ramp of 300°C/min until
650°C (top and bottom heat)
•Annealed at 650°C for 2min

•Plasma Ignited: 80W, 15kHz, 800V

•Pressure controller activated: Pchamber

= 6mbar
•Annealed under NH3 plasma for 3 min
while T raised to 750°C at rate of
200°C/min
•C2H2 (40sccm) introduced at end of
plasma anneal
•Growth time = 6min

•Plasma extinguished, cooled under N2

flow until T <400°C. Opened to
atmosphere

GTRI_B-14
Influence of Temperature on CNT growth
• Below 725 C – Catalyst does not sufficiently create „synthesis islands‟. Short, fat Carbon
Fiber like „CNTs‟ result
•Around 725 C – islands initiate growth, but rate of growth is limited
• 750 C - growth rate of ~0.3µm/min
• 775 C – some smaller islands, higher growth rate of smaller diameter CNTs
• 800 C – increased Ni diffusion into Si, few catalyst island remain on surface, sparse CNT
growth, much lower diameter. Rate is similar to 750-775 range with larger variance 650 C

675 C 700 C 725 C

750 C 775 C GTRI_B-15

800 C
Ion Electric Propulsion

G. Pirio, et al, Nanotechnology,

vol. 13, pp. 1-4, 2002.

Electron-induced
Surface Plasmon Resonance
(Chem-Bio Sensor)
MRE Antibodies

YYYYYGold Foil
Gate

CNTs

TiW/Mo/TiW electrode

GTRI_B-16
 84 Emitter Capacity
2.1 A at 25 mA/cm2
Busek BHT-200 Modified
for use with CNT Emitters
GTRI_B-17
Thrust!
GTRI_B-18
3D Solar Cells

GTRI_B-19
Multiple bounce light trapping
• Light Trapping= more absorbance

• Thinner layers = less recombination

• “orthogonalize” absorption and carrier extraction

• Solves “thick-thin” conundrum

GTRI_B-20
CNT-Based
Approach

• PR spun on

PR

Si

GTRI_B-21
CNT-Based
Approach

UV
• PR spun on
• Mask and expose to UV

Mask
PR

Si

GTRI_B-22
CNT-Based
Approach

• PR spun on
• Mask and expose to UV
• Develop PR

PR
PR

Si

GTRI_B-23
CNT-Based
Approach
• PR spun on
• Mask and expose to UV
• Develop PR
• Fe deposited

metal
PR
PR

Si

GTRI_B-24
CNT-Based
Approach
• Pattern generated on Si substrate via
photolithography
• Metal catalyst (Fe) applied
• Lift-off photoresist to leave only
patterned catalyst

metal metal

Si

GTRI_B-25
CNT-Based
Approach • Pattern generated on Si substrate via
photolithography
• Metal catalyst (Fe) applied
• Lift-off photoresist to leave only
patterned catalyst atop interconnect
layer
CNT CNT
“Tower” “Tower”
• CNT towers are formed in Chemical
Vapor Deposition (CVD) furnace
metal metal
(~720°C; 20 min.)

Si

GTRI_B-26
CNT-Based
Approach • Pattern generated on Si substrate via
photolithography
• Metal catalyst (Fe) applied
• Lift-off photoresist to leave only
patterned catalyst atop interconnect
layer

CNT CNT
• CNT towers are formed in Chemical
“Tower” “Tower”
Vapor Deposition (CVD) furnace
(~720°C; 20 min.)
metal p-type metal • p-type material (CdTe) applied via
Molecular Beam Epitaxy (MBE)
Si

GTRI_B-27
CNT-Based • Pattern generated on Si substrate via
photolithography
Approach • Metal catalyst (Fe) applied
• Lift-off photoresist to leave only
patterned catalyst atop interconnect
layer
• CNT towers are formed in Chemical
Vapor Deposition (CVD) furnace
CNT
“Tower”
CNT
“Tower” (~720°C; 20 min.)
• p-type material (CdTe) applied via
n-type
metal p-type metal Molecular Beam Epitaxy (MBE)

Si
• n-type material (CdS) applied via
MBE or CBD

GTRI_B-28
 • Pattern generated on Si substrate via
photolithography
CNT-Based • Metal catalyst (Fe) applied

Approach • Lift-off photoresist to leave only

patterned catalyst atop interconnect
layer
• CNT towers are formed in Chemical
Vapor Deposition (CVD) furnace
(~720°C; 20 min.)
• p-type material (CdTe) applied via
CNT
“Tower”
CNT
“Tower” Molecular Beam Epitaxy (MBE)
TCO • n-type material (CdS) applied via
metal
n-type
p-type metal MBE or CBD

Si • Transparent Conductive Oxide

applied via ion assisted deposition
(IAD)

GTRI_B-29
 • Pattern generated on Si substrate via
photolithography
CNT-Based • Metal catalyst (Fe) applied

Approach hu • Lift-off photoresist to leave only

patterned catalyst atop interconnect
layer
• CNT towers are formed in Chemical
Vapor Deposition (CVD) furnace
(~720°C; 20 min.)
• p-type material (CdTe) applied via
CNT
“Tower”
CNT
“Tower” Molecular Beam Epitaxy (MBE)
TCO • n-type material (CdS) applied via
metal
n-type
p-type metal MBE

Si
• Transparent Conductive Oxide
applied via ion assisted deposition
(IAD)

V
GTRI_B-30
 • Pattern generated on Si substrate via
photolithography
CNT-Based • Metal catalyst (Fe) applied

Approach hu • Lift-off photoresist to leave only

patterned catalyst atop interconnect
layer
• CNT towers are formed in Chemical
Vapor Deposition (CVD) furnace
(~720°C; 20 min.)
• p-type material (CdTe) applied via
Molecular Beam Epitaxy (MBE)
• n-type material (CdS) applied via
MBE
• Transparent Conductive Oxide
applied via ion assisted deposition
(IAD)

GTRI_B-31
 Molecular Beam Epitaxy for
CdTe and CdS deposition
(p/n junction)

CdTe

CNTs
CNTs
Si substrate

GTRI_B-32
GTRI_B-33
GTRI_B-34
 Light Reflection

3.0
Sample 1 Sample 4
2.5
Sample 2 Sample 5
Reflectance, R (%)

Sample 3 Sample 6
2.0

1.5

1.0

0.5

0.0
400 600 800 1000 1200 1400 1600 1800

Wavelength,  (nm)

GTRI_B-35
Extra Slides on CNT Batteries

GTRI_B-36
Silicon Battery

Si-coated Carbon Nanotubes

for Li - ion battery anodes
(with Yushin in MSE)
• Silicon has an order of magnitude greater
capacity compared to graphite anodes

• But Silicon has very poor cyclability

(pulverizes with Lithium insertion)

• Solution = Reinforce Silicon (with Carbon

Nanotubes)
1 5  kc
 1  Lix Si 5
Li   e   Si 
x 22 ka x 22

GTRI_B-37
 Vertically aligned carbon
nanotubes

Act as “rebar” to
strengthen internal
structure of Si-battery

Pictures of Si-coated
Carbon Nanotubes
Demonstrates conformal
coatings are possible

GTRI_B-38
 Charge/Discharge
Results • Stable performance and
reversible dealloying capacity
3000 100
in excess of 2000 mAh/g
2500 C-Si-VACNTs (over 5x more than graphite)
Dealloying Capacity (mAh/g)

80

Coulombic Efficiency (%)

2000
has been demonstrated.
60

1500
• VACNTs provide structural
1000
40
support for Si as well as
500 Theoretical capacity of graphite
20
dramatically improved
electrical conductivity
0
0 5 10 15 20
0
therefore higher power Si-
Cycle Number containing electrodes are
possible.

GTRI_B-39
 :
100 mm
•
• Sensors
• Cultures
• Scaffolds
• Heat Sink 20 mm

• Batteries
• Fuel Cells
• Logic circuits
• Hydrogen storage
• Waveguide/Filter
• Many, MANY more . . . 1 mm

GTRI_B-40