THORIUM FLUORIDE, ThF4
FOR OPTICAL COATING
Introduction
Thorium fluoride, ThF4, is the
currently preferred low index material which is transparent from the UV
to the IR. Evaporated films are durable and chemically stable and
exhibit low stress in thicknesses up to 2 µm. Common applications are
for AR coatings in the 8 to 12 µm region, including high power CO2
laser coatings.
Thorium fluoride is a naturally
radioactive material and must be handled and wastes disposed of in
accordance with state and/or federal regulations. In spite of special
precautionary measures needed with the use of ThF4, it still
is the premier coating material for lasers in the 8-12 µm region.
Deposition Suggestions
Thorium fluoride evaporates at 800°C. E-beam
or resistance-heated sources can be used. When using E-beam, slow,
gentle heating is advised. A molybdenum or tantalum hearth is suggested.
The recommended substrate temperature is 175°C, with a chamber pressure
below 10-5 Torr. A deposition rate of 10 Å/sec. minimum is
suggested. A greater rate is possible provided no spitting occurs.
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Optical Properties
Films at least 1000 nm thick are transparent
from approximately 250 nm to less than 11 µm. The refractive index in
the visible (550 nm) is 1.50. At 10 µm, the index is 1.35. Low substrate
temperatures and low deposition rates can cause water absorption bands
to appear near 3 µm and 6 µm in the IR.
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Applications in Multilayers
Thorium fluoride can be used as a component
in multilayer coatings for AR, bandpass and dichroic filters. The low
tensile stress of ThF4 and its good adhesion make it
compatible with ZnS, ZnSe, MgF2 and other fluoride compounds.
The microstructure of the deposited coating is amorphous, and the films
are relatively soft.
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A Note on Thorium Oxyfluoride
ThOF2 is a well characterized
compound, along with ThF4. However, it has been shown that
ThOF2 does not evaporate stoichiometrically, and all
resulting films are ThF4.*
*" Production and Properties of Vacuum
Evaporated Films of Thorium Fluoride," W. Heitmann & E. Ritter, Applied
Optics, Vol. 7, p. 307 (February1968).
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Production Process, Identification &
Purity
Thorium fluoride powder is prepared
chemically in a number of carefully controlled steps and melted under
inert or fluoride-based atmosphere to yield completely anhydrous ingots.
The unequivocal identification of ThF4 is made by X-ray
diffraction analysis, where patterns correspond to JCPDS Card No.
23-1426. The following table shows typical spectrographic analysis
results of ThF4.
|
Material
|
PPM
|
Material
|
PPM
|
|
Ce
|
n.d.
|
Sm
|
1.7
|
|
Dy
|
0.9
|
Tb
|
0.6
|
|
Er
|
7.0
|
Tm
|
n.d.
|
|
Eu
|
0.2
|
Yb
|
tr.
|
|
Gd
|
0.6
|
Cu
|
2.0
|
|
Ho
|
0.9
|
Fe
|
3.0
|
|
La
|
1.7
|
Mg
|
2.0
|
|
Lu
|
n.d.
|
Pb
|
3.0
|
|
Nd
|
2.6
|
Si
|
5.0
|
|
Pr
|
n.d.
|
Zn
|
5.0
|
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Radioactivity & Safety
Thorium fluoride and thorium oxyfluoride are
compounds containing naturally radioactive thorium. These radiochemicals
emit ionizing radiation, primarily in the form of alpha particles.
Thorium and its decay products, called thorium daughters, also emit some
beta particles and gamma radiation.
There is low risk of external radiation
exposure when handling generally licensed quantities of thorium
compounds (150 lbs or less per year and a possession limit of 15 lbs).
Radiation exposure to personnel should, however, be kept as low as
reasonably achievable. Inhalation or ingestion of all alpha emitters
should be avoided. The use of filter masks can be beneficial when the
possibility of airborne particulate radiation exists.
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Physical Data
|
Specific Activity of Thorium |
1.11 x 10-7
curies/gram |
| Physical
Half-life of Thorium |
1.39 x 1010
years |
| Physical
Half-life of Primary Daughter, Pb-212 |
10.64
hours |
| Annual Limits on
Intake of Thorium -232 (ALI) |
Oral: 7 x
10-1 uCi
Inhalation: 1 x 10-3 uCi
|
| Annual
Derived Air Concentration of Thorium -232 (Occupational exposure) |
5 x 10-13
µCi |
| Annual
Limits on Intake of Pb-212 (ALI) |
Oral: 8 x
101 uCi
Inhalation: 3 x 101 uCi |
| Annual
Derived Air Concentration of Pb-212 (Occupational exposure) |
1 x 10-8
µCi/ml |
| External
Radiation Exposure Limits (unrestricted area) |
2
millirems in 1 hour
100 millirems in 7 days
500 millirems per year |
| Estimation
of Radiation Exposure from Thorium |
1 lb. of
ThF4 in a pint can give a reading of about 0.5 mr/hr at
3.3 feet distance. |
| References |
Title 10
Code of Federal Regulations, Parts 20 and 40 |
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