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JOURNAL OF NUCLEAR MATERIALS 9, No. 1 (1963) 59-64, NORTH-HOLLAND PUBLISHING CO.

, AMSTERDAM

ISOTROPY OF SURFACE PROPER~S OF ~~-~~~:


I. ANISOTROPY OF CATHODIC ETCHING

Yu. N. SOKURSKI, F. P. BUTRA, 0. L. FUFAEVA and K. A. USTAVSHIKOVA

Academy of Sciences of the USSR, .Moscow

Received 10 January 1963

Cathodic etching of uranium has been studied in an argon Les &ultats exp~rimen~ux sont expliqik qualitative-
atmosphere. The an~otropy of etching has been judged ment en se hasant sur le concept de collisions converge&es
by the relief produced on the surface of polycrystalline sur une propagation preferentielle dun moment dans le
a-uranium specimens. The surface of crystal&es close to reseau suivant les directions les plus compactes et sur la
the crystallographic planes { IOO], {llO} has been shown faible probabiliti de l’inversion du moment dans ce eas.
to have the minimum rate of etohing, while those close to Des experiences complementaires sur l’attaque cathodique
(021) have the maximum rate. The relative differenoe du cuivre conduisirent & des r&&tats qui sont en bon
between these extreme values of the etching rate amounts accord aveo l’explication ci-dessus.
to 40%. ---
The experimental results are qualitatively accounted for Es wird das kathodische Atzen von Uran in einer Argon-
on the basis of the concept of focus&g collisions, a pre- atmosph&reuntersuoht. Die Anisotropie der Atzung wmde
ferred propagation of momentum into the lattice along nach dem Relief beurteilt, das auf der Oberflaohe des poly-
close-paoked directions and the small p~bab~ty of the k~~~~en a-Urans e&&and. Die ~~i~~~chen
reversal of momentum in this case. Ad~~onal experiments mit den~~~ograph~chen Ebenen { IOO),{llOf zeigen den
on the cathodic etching of copper yielded results which kleinsten Atzangriff, die k~sta~og~phisehe Ebene (0211
are in good agreement with the above explanation. dagegen den g&&en. Die relative Differenz zwischen
diesen beiden Extremwerten des Atzangriffs betriigt 40%.
L’attaque cathodique de l’uranium a Bt6 Btudiee en atmo- Die experimentellen Ergebnisse werden qualitativ aus-
sphere d’argon. L’anisotropie de l’at,taque a Bt(, jug&e par gewertet auf der Grundlage des Konzepts der fokus-
le relief produit B la surface d’echantillons polycristallins sierenden ZusammenstijSe, einer bevorzugten Verteihmg
d’uranium o(. La surface des oristaux d’orientation voisine eines Impulses im Gitter entlang der dicht gepackten
des plans cristallographiques { 100 }, { llO> presente la Richtungen und entsprechend der geringen Wahrschein-
vitesse minimale d’attaque tandis que ceux proches de {021> lichkeit einer Umkehrung dieses Impulses. ZuslltrJiche
ont la vitesse maximale. La difference relative entre ces Experimente fiber das kathodische Atzen von Kupfer
valeurs extremes de la vitesse d’attaque s’eleve ii environ befinden sich in guter ~bereinst~mung mit dieser Er-
40%. kl&rung.

1. Introduction uranium section were revealed not in the form of


A mmrber of papers have been published on the grooves; instead, steps developed at the boundaries,
technique of cathodic etching of uraniuml-a). In resulting from a difference in the rate at which
some instances the cathodic etching of uranium differently oriented grains were etched. The data
has some advantages over conventional etching obtained made it possible to draw certain tentative
techniques, and therefore a comprehensive study conclusions concerning the relationship between the
of the potentialities of the method is of considerable rate of etching by ion bombardment and the crystal
interest. structure of uranium. The anisotropy of the
While studying the structure of cath~cally cathodic etching of copper was also investigated in
etched uranium, the authors noted that under the order to confirm these conclusions.
etching conditions used the grain boundaries on a The anisotropy of the oxidation of cath~cally
60 Yu. N. SOKURSKI, F. P. BUTRA, 0. L. FUFAEVA and K. A. USTAVSHIKOVA

and electrochemically etched uranium has also been current, (3500 volts, 2 mA current, gas pressure of
studied. The results of t’his investigation will be 8 x 10. 3 torr). The time of etching was 30 to
given in the next paper of the series. 40 minutes. The average thickness of the sputtered
layer was determined from a weight loss of t,he
2. Experimental Technique specimen and was equal to about 30 ,um. The height
The work was done on zone-refined uranium. of the grain boundary steps (fig. 2) resulting from
The metal was rolled into 70 x 4 x 0.3 mm strips. t’he difference in the rate of et,ching different]!
The strips were heated to 730” C in evacuated
quartz capsules, held at this temperature for one
hour and water-quenched ; they *were then sub-
jected to recrystallization-annealing at 640-650” C
for 40-60 hours. In this way coarse perfect grains

Fig. 1. Schematic view of the apparatus for cathodic Fig. 2. Photomicrograph of the relief formed on a surface
vacuum etching. -- of an alpha-uranium specimen on cathodic etching. Y 506
I- Specimen; 2 - copper disk; 3 - liquid-nitrogen-cooled
copper block; 4 - tube for argon supply; 5 - vacuum bell
jar; 6 -insulating glass tubes and plates; 7 -tube for oriented grains was measured. As can be seen from
pouring liquid nitrogen. the figure, the surface of the ion- bombarded grains
remains quite smooth as a rule. However, in some
0.5-2 mm in size were grown in the strips. Speci- cases etch-figures with a specific “lamellar” ap-
mens lo-12 mm long were machined from the pearance were observed on the surface. The surface
strips, and one surface of each such coarse-grained of the ion-bombarded specimen remained quit,tt
sample was ground, polished and etched. bright. The contrast in tints (fig. 2) is due to a slight
All the operations were carriedoutin such amanner oxidation of the specimen in air after cathodic
as to minimise the deformation of the specimens. etching.
The orientations of the grains were determined for The height of the steps was measured by a
four selected specimens (approximately 30 grains Linnik interference microscopel) with an accuracy
per specimen), by means of back-reflection X-ray of _e 0.3 pm. Fig. 3 shows an interference photo-
diffraction patterns. micrograph of the relief revealed by cathodic
The orientation of the grains having been etching. The height of the grain boundary st,eps
determined, each specimen was repolished electro- was determined from the number of t,he inter-
lytically and then placed into an apparatus for ference lines crossed in traversing each step.
cathodic etching (fig. 1). The sample (1) was fastened The anisotropy of cathodic etching was charac-
with a polymerizing adhesive to a massive copper terized by the coefficient of the relative etching
disk (2), which was inserted into a liquid-nitrogen- ability K = h/h,,, where h,, is the average thick-
cooled copper block (3). Cathodic etching was ness of the sputtered layer on the whole specimen
carried out in an argon atmosphere by a direct and h is the depth of etching on a. particular grain.
ANISOTROPY OF CATHODIC ETCHING 61

The difference in the values of K for the main


regions of weak-f lOO), (llO)-and strong- (021}-
etching amounts to 40%) which is well above the
accuracy of determination of K (within I_t3%).
Thus, if two grains, the orientations of which fall
within these two regions with extreme values of K,
are adjacent, then with the mean depth of etching
amounting to 30,um, the step on the boundary
between them will be 12,um.
Such an anisotropy of cathodic etching cannot be
accounted for by the passivation of the uranium
grains in the process of ion bombar~ent. In our
Fig. 3. Interference photomicrograph of the relief formed experiments special precautions were taken to sup-
on cathodically etched n-uranium. The photograph wae press the formation of a passivating film (chemically
taken using a Linnik interference microscope. x 400 pure argon and liquid nitrogen traps to freeze
out vapours were used ; the specimen was specially
The differences in the relative etching abilities of cooled). Therefore, no indications of surface oxida-
adjacent grains were measured in the experiments. tion were observed, and after etching the specimens
The measured differences for all the possible eom- remained quite bright. Besides, the investigations
binations of grain pairs were then normalized, of the anisotropy of the oxidation after cathodic
takiug into account the average thickness of the etching showed that in a number of cases the
sputtered layer, and absolute values of the coeffi- greatest etching ability was chara~~~stic of the
cient K were thus defined. The results were plotted grains which oxidize rather easily.
on the standard crystallographic projection. The anisotropy of etching by ion bombardment
The etching technique for copper and the treat- might be attributed to an orientation dependent
ment of the results were the same as for uranium. on the rate of atomic evaporation consequent on
local heating up of an ion-bombarded metal surface.
However, this explanation is unlikely. Such a strong
3. Results and Discussion
anisotropy of the rate of the evaporation of uranium
The orientations of more than 100 grains were atoms as would be necessary to account for the
found and the values of the coefficient of relative
etching ability K were measured for all these grains.
The results are presented on a standard stereo-
graphic projection of a uranium lattice (fii. 4). The
points in this figure denote the pole of the in-
vestigated surfaces of the grains. The coincidence
of these poles with one or another pole of the
crystallographic plane indicates that this crystallo-
graphic plane coincides with the investigated sur-
face of a particular grain.
As can be seen from the figure: the largest region
of very weak etching is found to be near the
(100 > and {llO> poles. The smaller zones of very
weak etching are near the (11 l> and ( 1511 poles. Fig. 4. Anisotropy of the cathodic etching of a-urauium.-
v w - very weak etching, K = 0.75-0.85;
The main region of strong etching is found near
w-weak etching, K = 0.90-1.00;
the (021) p o1e,._smaller zones of strong etching are m - medium etching, K = 1.00-1.05;
near the (243) and (204) poles. s -strong etching, K = 1.05-1.15.
62 Yu. N. SOKURSKI, F. P. BUTRA, 0. L. FUPBEVA and K. A. USTAVSHIKOVA

detected effects, was not observed on vacuum- from a metal surface it is necessary to know the
heating uranium. atomic interaction potential in a uranium lattice
Therefore, another explanation given below and to solve the corresponding many-body problem
seems more probable. This explanation is based on in a manner similar to that used by Vineyard et al.
a consideration of the mechanism of interaction of for copper5). However, a qualitative notion of the
fast ions with the atoms of a crystal lattice, in the probability of these processes can be obtained by
light of recent work on the dynamics of radiation considering the effect of the arrangement of uranium
damage 5--7). The acceleration of ions in a cathodic atoms in planes normal to a bombarded grain
discharge occurs preferentially in the zone of the surface on the probability of a momentum reversal.
cathodic potential drop. In our experiment,, the The planes of a uranium lattice corresponding
value of the cathodic potential drop was not, to t’he orientation regions of maximum and mini-
measured specially. If one assumes that it measures mum etching are shown in fig. 5. As can be seen
approximately half of the applied potential, then from fig. 5a, in cases when the grain surface is
the energy of the bombarding ions will be N 1800 eV . formed by planes close to {loo}, the close-packed

while the average energy E available for transfer rows of the atoms: arranged along an (100) axis.

to an uranium atom will be N 400 eV. If the simple will be almost normal to the surface. They arc

theory of radiation damages is used for this case. shown by dashed lines in fig. 5a. Now, the momen-

then the number of displaced atoms per incident tum transfer in a lattice is well described by Sils-
bee’s concept of focus&q collisiod). Focussing
ion should be N Ej2Ed = 8 atoms/ion, where Ed
collisions should take place when 1) 5 4R, where
is a threshold energy for the atomic displacement.
I) is an interatomic spacing ancl R is an effecbivc
assumed to be 25 eV.
atomic collision radius. Since R decreases with an
In reality, this value is too low. Since in this increase of the energy of an atom, the focussing con-
case the momentum is transferred to the surface
atoms, for the displacement of which an energy
less than Ed is required, the effective number of the
displaced atoms should be higher. However, in
cathodic etching the momentum of a bombarding
ion is generally normal to the surface being
irradiated and is directed into the specimen, while
the momentum of the sputtered atoms is directed
towards the outside of the specimen, Hence, for
evaporation from the metal surface to proceed, a
momentum reversal is necessary; such a reversal
can take place due to a large number of the atoms
of a crystal lattice participating in the process of
collisions. The value of the coefficient of the relative
etching ability is likely to be defined by the proba-
bility of such a momentum reversal for a particular
crystallographic direction. Momentum reversals are
likely to occur rather rarely. Indeed, t,he average Fig. 5. Schematic representation of momentum transfer
experimental yield of sputtered atoms was 2.4 atoms/ in an *-uranium lattice.

ion, i.e., about 30% of the minimum number of the a) - in cross-section normal to a (100) plane (weak etching);
b) -in a cross-section normal to a (021) plane (strong
displaced atoms that was calculated using the
etching).
simple cascade theory.
(Black circles indicate atoms that are in the plane of the
To quantitatively estimate the probability of a diagram; light circles are atoms in adjacent planes, close-
momentum reversal and a knock-out of an atom packed directions are designated by dashed lines).
ANISOTROPY OF CATHODIC ETCHING 63

ditions are ~~~~ only when the energies are are shown in fig. 6. The planes the orientation of
sufficiently low. The potential of the atomic inter- which is close to (110) have the lowest rate of
action in the alpha-uranium lattice is unknown. etching. The planes approximately parallel to cube
However, it may be assumed that owing to the { 100) or octahedral { 1111 faces showed the
large number of electrons in a uranium atom, its maximum rate of etching.
effective radius will decrease with the growth of In the face-centered cubic lattice the close-
the energy of colliding atoms more slowly than, for packed directions (IlO} are normal to (IlO> planes.
instance, in the case of copper. Thus, in the present Hence, the above explanations of the anisotropy
experiments when g is approximately 400 eV, the of the cathodic etching of alpha-uranium may be
conditions under which focussing collisions arise applied to copper as well. In this case the slow rate
may be assumed to be satisfied for a considerable of etching of the { 110) planes appears to be again
number of primary displaced atoms and for the consequence of the momentum transfer inside
practically all the secondary displaced atoms.
Thus, as fig. 5 shows, on ion-bombarding (100)
or {LlO) planes, the momentum received by a
surface atom will be transferred inside the lattice
along the close-packed direction [lOOJ, and will not
suffer a reversal.
There is no doubt that there exists a certain finite
probability of a momentum reversal, e.g. in the
case of a glancing collision of an ion with an atom,
when the latter will receive a moments in a Fig. 6. Anisotrepy of the cathodic etching of copper. -
direction inclined to the surface normal. However, w - wmk etching, R N 0.65;
m-mean etching, K N 1.00;
during such collisions a lower energy is transferred
s -strongetching, K N 1.20.
and their influence on the etching process will be
smaller.
the lattice along the close-packed directions and
A different situation should take place on bom-
of the small probability of its reversal.
bardiug grains the surface of which is formed by
Recently there were published some data on the
planes of (021) type. In this case the close-packed
anisotropy of cathodic etching a single crystal of
rows are strongly corrugated and inclined to the
coppers). The single crystal was irradiated with a
grain surface (fig. 5b). Because of this, the f~~s~g
parallel ion beam at different angles of incidence
collisions do not occur. This is qua~~tively
on the crystal surface. This work also showed that,
illustrated by the scheme of a momentum transfer
the minimnm in the rate of cathodic etching fell
shown in fii. 5 b. It shows that in this case the
on the close-packed directions. Thus, the explanation
process of the momentum reversal is a logical conse-
suggested above is generally applicable to these
quence of the corrugation of the close-packed rows.
experiments too.
Thus, according to the above conceptions, the
probability of a momentum reversal on the ion- 4. Conclueiom
bombardment of (100) planes is smaller than The investigation of the cathodic etching of alpha-
on the bombardment of (021) planes. This is in uranium showed that the rate of etching is strongly
agreement with the experimentally observed rela- dependent upon the ~rysta~o~aphie direction. The
tionship between the etching rates. planes close to (021) have the highest rate of
To confirm the above theoretical conceptions, etching, while those close to (100) and ( IlO> have
the cathodic etching of copper was investigated. It the lowest rate. An attempt has been made to
was found that in this case the rate of etching is account for the anisotropy of the cathodic etohing
also anisotropic. The results of the investigation from the point of view of the present theory con-
64 Yu. iT. SOKURSKI, F. I’. BUTRA, 0. L. FUFAEVA and K. A. URTAVYHIKOVA

cerning the radiation damage mechanism. The References


lower etching ability of the (100) planes can be ‘) A. X. Holden, Physical Metallnrg~ of Vraniuzn(Addi-
accounted for by the transfer of momentum into son- Wesley, 1958)
the lattice along the close-packed directions which ‘) S. ‘I’. Konobeevski, K. P. Dubrovin. B. M. Levitski,
result,sin a decrease of the probability of mo~~entum L. D. Panteleev, H. F. Pravdyuk, Second Geneva Con-
reversal, which is required to remove an at,om from ference, P/2192 (1958)

the surface. 3, M. Aeam, Mem. Scient. Rev. _N&. 41


1 (1960)
To check the validity of such an explanation
“) \:. P. Linnik, Dokl. Akad. Nauk SSSR 6 (1933) 18
experiments were performed with the cathodic
5, J. B. Gibson, A. N. Goland, M. Milgram and G. H.
etching of copper. (110) planes normal to close-
Vineyard. Pbys. Rev. 120 (1960) 1229
packed directions ( 110) were found to have the
minimum rate of etching. The results obtained for 6, R. H. Silsbee, J. Appi. Phys. 28 (1957) 1246
copper are in good agreement, with t,he a,bove ‘) M. W. Thompson, hTuc1.Eng. 18 (1960) 133
notions concerning the mechanism of t.he cathodic “) V. A. MoIehanov, V. CT.Telkcvsky, V. Y. Chicherov,
etching of a-uranium. Dokl. dkad. Nauk SSSR I37 (1961) 58