Effective dry etching process of actinide oxides and their...

Details Effective dry etching process of actinide oxides and their... Effective dry etching process of actinide oxides and their...

2002-04-01

2004-03-02

Norton, Nadine G. (Department: 1765)

Etching a substrate: processes

Heating or baking of substrate prior to etching to change...

C216S058000, C216S063000, C216S067000

Reexamination Certificate

active

06699398

ABSTRACT:

TECHNICAL FIELD
This invention relates to an effective dry etching process of actinide oxides and their mixed oxides in CF
4
/O
2
/N
2
PLASMA.
BACKGROUND OF THE INVENTION
The fluorination of uranium dioxide has been extensively studied in the application-oriented fields such as uranium separation, processing, and conversion. Along with the applied research, fundamental studies of the UO
2
/F
2
reaction have been reported by several authors [T. Yahata and M. Iwasaki,
J. Inorg. Nucl. Chem.
26 (1964) 1863, G. Vandenbussche, CEA-R 2859 (1966), M. Iwasaki,
J. Nucl. Mater.,
25 (1968) 216, J. C. Batty and R. E. Stickney,
J. Chem. Phys.,
51 (1969) 4475, B. Weber and A. Cassuto,
Surf. Sci.,
39 (1973) 83, A. J. Machiels and D. R. Olander,
High Temp. Sci.,
9 (1977) 3].
The reaction of UO
2
at low temperatures of below 800 K under atmospheric pressure of F
2
was studied using weight loss measurements by Vandenbussche [G. Vandenbussche, CEA-R 2859 (1966)] and by Iwasaki [M. Iwasaki,
J. Nucl. Mater.,
25 (1968) 216]. Under these conditions the ultimate reaction products are found to be UF
6
and O
2
, while a variety of intermediate reaction products such as (UO
2
)
4
F and UO
2
F
2
are identified. On the contrary, a quasi-equilibrium reaction modelling study predicted that at high temperatures of above 1000K under low pressure of F
2
(10
−7
~10
−4
Torr), uranium hexa- and penta-fluoride formations are suppressed in favor of UF
4
and atomic fluorine formation [J. C. Batty and R. E. Stickney,
J. Chem. Phys.,
51 (1969) 447, and B. Weber and A. Cassuto,
Surf. Sci.,
39 (1973) 83].
A kinetic study carried out later at high temperatures of above 1,000 K under ultra-high vacuum condition confirmed that the reaction product is UF
4
and the reaction probability is about 10
−2
[A. J. Machiels and D. R. Olander,
High Temp. Sci,.
9 (1977) 3]. The authors claimed that the reaction mechanism is a second-order surface reaction coupled with the double-diffusion process. The disagreement between these early experimental results seems to stem from the different ranges of temperatures and pressures.
Recently the feasibility of burning spent PWR fuel in a CANDU reactor was carried out, in which decladding of spent fuel pins and dry-processing of burned uranium dioxide such as OREOX (Oxidation and Reduction of Oxide fuel) process are the main processes to make re-sinterable fuel powder [H. Keil. P. Boczar. and H. S. Park,
Proc. Intern. Conf. Tech. Expo. on Future Nuclear Systems, Global
'93. Seattle, Wash., USA [Sep. 12-17, 1993) 733 and M. S. Yang. Y. W. Lee. K. K. Bae. and S. H. Na.
Proc. Intern. Conf. Tech. Expo., on Future Nuclear Systems, Global
'93. Seattle, Wash. USA (Sep. 12-17, 1993) 740]. In the process, however, most candidate decladding techniques were unable to recover more than 98 to 99.5% of the heavy metal/metal oxide. A part of the remainder will be present as adherent dust and some may also be chemically bonded to the zirconium oxide layer on the inside of the fuel pin. Therefore, another process for additional removal of the last portion of the fuel is required, which also removes alpha contamination from the clad to a level qualifying the fuel hulls as non-TRU. For the secondary decontamination process, a plasma processing technique using fluorine-containing gas plasma was proposed and its applicability has been demonstrated [Y. Kim. J. Min, K. Bae, M. Yang, J. Lee. and H. Park,
Proc. Intern. Conf. on Future Nuclear Systems, Global
'97. Yokohama, Japan (Oct. 5-10, 1997) 1148]. Since then, dry etching treatments of TRU oxide including uranium dioxide have been extensively focused.
Following the demonstration, as a representative compound of actinide oxides including TRU dioxides, the effective etching reaction process of uranium dioxide in CF
4
/O
2
/N
2
plasma and reaction mechanisms have been investigated in detail in this work.
SUMMARY OF THE INVENTION
It is invented that the fluorination etching reaction of actinide oxides such as UO
2
, ThO
2
, and PuO
2
in CF
4
/O
2
gas plasma is enhanced when small amount of N
2
gas is added or mixed at the temperature of ambience up to 600° C. under the low pressure of 1 m Torr up to 1 atm. As a representing actinide, oxide uranium dioxide was chosen and its reaction rates were investigated as functions of CF
4
/O
2
/N
2
ratio, plasma power, substrate temperature, and exposure time to the plasma. From the current investigation, it is found that there exists an optimum CF
4
/O
2
ratio for the effective etching in CF
4
/O
2
/N
2
plasma. The ratio of CF
4
to O
2
is around four, regardless of plasma power, substrate temperature, and gas volume flow rate. When the small amount of N
2
gas ranging from 1% to 20% of CF
4
gas based on the gas volume is added to or mixed with the optimized CF
4
/O
2
the etching rate is enhanced remarkably over 4 up to 5 times compared to that of CF
4
/O
2
plasma without N
2
gas.
This optimum etching process must be applicable to the dry etching of other actinide oxides including TRU (TRans-Uranium) oxides and their mixed oxides since all actinide elements have very similar chemical characteristics with uranium and, thus, form similar types of oxides.
In current examination, r.f. and microwave power gas plasma generation techniques were used with the power ranging 50 W up to 2 kW and the effectiveness of this process was confirmed. Since basic principle of gas plasma generation techniques is identical except different working pressure ranges, this effective etching rate must be increasing with increasing plasma power up to 100 kW extractable from various gas plasma generation techniques such as dc (direct current), ac (alternating current), and ecr (electron cyclotron resonance) plasma.
Also the effectiveness of this process was successfully demonstrated in the etching experiments of uranium oxide on the zirconium alloys, stainless steels, or inconels (Ni based alloys) substrates.


REFERENCES:
patent: 6171511 (2001-01-01), Charollais et al.
Kim et al., “Dry etching of U and UO2 by flourine containing gas plasma” Proc. Intern. Conf. on Future Nuclear Systems Global '97, p. 1148-1150), Japan (Oct. 5-10, 1997).

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