Fabrication and Properties of

Ultranano, Nano, and

Polycrystalline Diamond
Membranes and Sheets
D. K. Reinhard, M. Becker, R. A. Booth,
T. A Grotjohn, T. Schuelke, and J. Asmussen
Michigan State University &
Fraunhofer Center for Coating
and Laser Applications.
Motivation: Electron Stripping
Foils for Heavy Ion Beams

Presentation:
1. Film synthesis
2. Post
processing &
fabrication
3. Properties
 Definitions
For purposes of this presentation:
• Polycrystalline: grain sizes measured in micrometers
• Nanocrystalline: Sub-micron grains; grain sizes
measured in hundreds of nanometers
• Ultrananocrystalline: Grain sizes measured in tens of
nm and smaller; fabricated with Ar/CH4 chemistries. *

* D. M. Gruen, Annu. Rev. Mater. Sci., 29, 211, (1999).

 Film Synthesis
• Nucleation on silicon wafers is facilitated by
pre-treatment with diamond powder (< 0.25µm).
Polycrystalline: Diamond powder is mixed with
resist and wafer is spin coated. Nanocrystalline
& Ultrananocrystalline: Diamond is dry-
polished with powder and cleaned.
• Deposition is by 2.45 GHz microwave plasma-
assisted chemical vapor deposition using tunable
microwave cavity reactors operating in the TM012
mode.
 Deposition Parameters:
poly- and nanocrystalline
• Pressure: 7 – 15 torr (poly); 15 – 35 torr (nano)

• Microwave Power: 700 W

• Typical Gas Flow Rates:
H2 200 sccm
CO2 8 sccm
CH4 3 sccm
• Substrate Temperature: 500 - 600°C (poly);
600 - 700°C (nano)
 Ultrananocrystalline Deposition
Parameters
• Pressure: 120 torr
• Microwave Power: 1.1 KW, PINC – PREF
• Typical Gas Flow Rates:
Ar 100 sccm
H2 1 to 4 sccm
CH4 1 sccm
• Substrate Temperature: < 650 C.
Electron Stripping Foil Fabrication
1. The diamond-coated silicon substrate is cut to the
desired size of the final foil. The silicon is removed
by wet etching.
2. The free diamond sheet is removed from the
etching solution and either used directly or stored
for later use.
3. The diamond sheet is placed on the new substrate
or frame. In the case of the electron stripping foils,
the diamond sheet is held in place by a carbon based
adhesive (TMAquadag M)
Diamond foils on 4-sided frames

1.2 cm
Nano Poly
Diamond foil on 3-sided frame.
Nano Ultranano

1 cm
Diamond sheet with 1-side
support
Diamond sheets are Post-Processing
flexible when wet.
Draped on
Observations
tweezer.
…and can be wrapped
around cylinders.

360° diamond wrap

The sheets can be applied ¼” SS tube

to curved surfaces …

Lens
 Post-Processing Observations,
cont.
Surface tension allows thin sheets
to be floated in aqueous solutions.
Dried diamond sheets
can be lifted and placed
electrostatically.

Sheets can also be transferred to frames and substrates in the

solution. Dried sheets replaced in solution regain their
flexibility.
 Diamond Sheet Properties
• Microstructure (SEM, AFM)
• Optical (transmission: infrared, visible,
ultraviolet).
• Mechanical (fracture strength).*

*Please see paper TF-WeP30, Grotjohn et

al. for additional discussion of mechanical
properties.
 Micrograph of poly film
S52 SEM
1332 cm-1 Raman

H2/CO2/CH4 (sccm): 200/8/3. Power = 0.7 kW, P = 15 torr

Resist Seeding
 Micrographs of nano film
FB16 SEM AFM

500 nm
1 µm
H2/CO2/CH4 (sccm): 200/8/3. Power = 0.7 kW, P = 33 torr
Polished Seeding
 Micrographs of ultranano film
SEM AFM

1µm 1µm
Ar/H2/CH4 (sccm): 100/1/1. Power = 1.1 kW, P = 120 torr
Polished Seeding
 IR to UV Transmission
100
% Transmission

80
60
40
20
0
0 1000 2000 3000
Wavelength (nm)

Nanocrystalline: FB24
 UV Absorption Cut-off
40
% Transmission

Scatter limited by
30 surface roughness
20

10

0
3 4 5 EG 6 7
Energy (eV)

Nanocrystalline: FB24
 Fracture Strength

Pressure Ni
metal metal
diamond membrane
epoxy epoxy
metal
Atmosphere metal

Measure: Burst pressure.

  
 
 σ UTS  t 
Burst Pressure PB =
 E  a 
 0.204 
 1−υ 

σUTS: ultimate tensile strength (film center)

E: Young’s modulus
υ: Poisson’s ratio
a: membrane radius
t: membrane thickness
PB: burst pressure.

Pickhardt and Smith, JVST, 14, 823, 1977

Cardinale and Robinson, J. Mater.Res., 7, 1432, (1992)
 Burst Pressure Correlation with t/a
For natural diamond* with E =
1050 GPa, ν = 0.1 σUTS = 2.8 GPa
250

200
O - ultra
Burst Pressure (psi)

150 x - nano
100 + - poly

50

0
0.5 1 1.5 2 2.5
t/a ratio -3
x 10

*The Properties of Diamond, J. E. Field, Assoc. Press, London, 1979

 Summary
• Free-standing thin film diamond sheets and
membranes are applied by post-processing to a
variety of substrates and frames.
• The sheets are drapable, and can be applied to
curved surfaces and wrapped around cylinders.
• The sheets show considerable strength. A 0.97
µm thick ultranano sheet mounted as 2 mm
diameter membrane showed a burst pressure of
79 psi (547 kPa). Implied fracture strengths can
be comparable to natural diamond.