U.S. patent number 3,644,044 [Application Number 05/038,961] was granted by the patent office on 1972-02-22 for method of analyzing a solid surface from photon emissions of sputtered particles.
This patent grant is currently assigned to Bell Telephone Laboratories Incorporated. Invention is credited to Norman Henry Tolk, Clark Woody White.
United States Patent |
3,644,044 |
Tolk , et al. |
February 22, 1972 |
METHOD OF ANALYZING A SOLID SURFACE FROM PHOTON EMISSIONS OF
SPUTTERED PARTICLES
Abstract
Identification of unknown constituents and their relative
concentrations in a solid surface is made by bombarding the solid
surface with an ion or molecule beam having low energy and low
density, so as to achieve the sputtering of excited particles
directly from the surface and resultant photon emissions
characteristic of the sputtered particles.
Inventors: |
Tolk; Norman Henry (Westfield,
NJ), White; Clark Woody (Dover, NJ) |
Assignee: |
Bell Telephone Laboratories
Incorporated (Murray Hill, NJ)
|
Family
ID: |
21902914 |
Appl.
No.: |
05/038,961 |
Filed: |
May 20, 1970 |
Current U.S.
Class: |
356/314; 850/43;
250/358.1 |
Current CPC
Class: |
H01J
37/252 (20130101) |
Current International
Class: |
H01J
37/252 (20060101); H01j 037/26 (); G01j
003/30 () |
Field of
Search: |
;250/49.5P,71R
;356/85 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Birch; Anthony L.
Claims
What is claimed is:
1. A method for determining the identities and relative
concentrations of constituents of a solid surface comprising:
1. producing collisions of incident particles with the solid
surface with sufficient energy to sputter particles from the
surface, in an excited state to obtain photon emissions from at
least a portion of said sputtered particles;
2. detecting at least a portion of the photon emissions so as to
obtain electrical signals; and
3. processing the signals so as to obtain at least a portion of a
characteristic spectrum, the wavelengths at which spectral peaks
occur indicating the identity of the constituents, and the
intensities of the peaks indicating the relative concentrations of
the constituents;
characterized in that said incident particles are in the form of a
beam.
2. The method of claim 1 in which the collisions occur at an energy
of at least 3 to 5 electron volts in excess of the energy defined
by the relationship
where m.sub.1 is the mass of the incident ion or molecule, m.sub.2
is the mass of the sputtered atom, E.sub.s is the threshold energy
for the sputtering of surface atoms in their electronic ground
states, and E* is the excitation energy of a specific excited state
of the sputtered atom.
3. The method of claim 2 in which the collision occurs at an energy
of from 100 to 4,000 electron volts.
4. The method of claim 1 in which the particle beam consists of
ions of a member selected from the group consisting of nitrogen and
the rare gases helium, neon, argon, krypton and zenon.
5. The method of claim 1 in which the solid surface is contacted by
a conducting grid.
6. The method of claim 1 in which a conducting grid is positioned
adjacent the solid surface.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method and apparatus for analyzing
solid surfaces by means of low-energy collisions with a low-density
gaseous particle beam to produce characteristic spectra.
2. Prior Art
In the field of chemical analysis, a simple method for the
nondestructive testing of solid surfaces has been long desired, but
is still an elusive goal. For example, one recently developed
technique involves focusing a laser beam on a small selected area
of the surface to be analyzed so as to remove a portion of the
surface by vaporization, thereby leaving behind a crater which may
be large enough to be visible to the unaided eye. The vapor is
subsequently analyzed spectroscopically. Another nondestructive
test technique is sometimes referred to as hollow cathode
discharge. Briefly, the principle of operation of hollow cathode
and similar glow discharge apparatus is as follows. A potential is
developed between an anode and a cathode in an inert gas
atmosphere, e.g., Ne at 16 to 20 mm. of Hg; a glow discharge
results from the collision and excitation of the gas with
electrons. A sample placed near the cathode, e.g., inside a hollow
cathode, gives up particles as a result of bombardment by the
surrounding gas, and at least some of these particles are then free
to participate in the glow discharge by collision with electrons.
Knowledge of the surface may then be gained by an analysis of the
glow discharge. However, in order that a significant portion of the
glow discharge be due to particles from the sample surface, a
relatively large amount of material must be removed from the
surface. Such removal leads to large power consumption, and
possible thermal damage to the sample.
The search continues for a simple and effective technique for the
nondestructive chemical analysis of solid samples.
SUMMARY OF THE INVENTION
According to the invention it has been discovered that bombardment
of solid surfaces with ion or molecule beams which may be of low
energy and low density, results in the sputtering of excited
particles directly from the surface. Resultant photon emissions
from the sputtered particles in the vicinity of the surface are
characteristic of the constituents of the surface and the
intensities of the spectral peaks are related to the number of
collisions, thus enabling identification of unknown constituents
and their relative concentrations in the surface.
Devices of the invention are notable for their simplicity and are
particularly useful in applications requiring low weight and low
power consumption. According to a preferred embodiment, spectra are
obtained by first directing an ion beam of nitrogen or a rare gas
through an ion electrostatic lens into a sample chamber and against
the surface to be analyzed, and then detecting resultant photon
emissions over a preselected band of wavelengths using single
photon counting techniques.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic diagram of a preferred embodiment of the
inventive apparatus;
FIG. 2 is a graph of intensity versus wavelength for the photon
emissions resulting from the collision of He.sup.+ ions with a
nickel surface;
FIG. 3 is a graph similar to the graph of FIG. 2 for the collision
of N.sub.2 .sup.+ ions with a nickel surface;
FIG. 4 is a graph similar to the graph of FIG. 2 for the collision
of Ar.sup.+ ions with a nickel surface;
FIG. 5 is a graph similar to the graph of FIG. 2 for the collision
of N.sub.2 .sup.+ ions with a copper surface; FIG. 6 is a graph
similar to the graph of FIG. 2 for the collision of Ar.sup.+ ions
with a copper surface;
FIG. 7 is a graph similar to the graph of FIG. 2 for the collision
of Ne.sup.+ ions with a copper surface;
FIG. 8 is a graph similar to the graph of FIG. 2 for the collision
of N.sub.2 .sup.+ ions with a germanium surface;
FIG. 9 is a graph similar to the graph of FIG. 2 for the collision
of Ar.sup.+ ions with a germanium surface;
FIG. 10 is a graph similar to the graph of FIG. 2 for the collision
of N.sub.2 .sup.+ ions with a silicon surface;
FIG. 11 is a graph similar to the graph of FIG. 2 for the collision
of Ar.sup.+ ions with a silicon surface; and
FIG. 12 is a graph of excitation cross section versus ion energy
for N.sub.2 .sup.+ ions bombarding a nickel surface.
DETAILED DESCRIPTION OF THE INVENTION
For convenience, the method will be described according to a
preferred embodiment. The first two steps of ion collection and ion
focusing involve considerations and techniques well known to those
skilled in the art of mass analysis. In general, however, it may be
stated that the purpose of the collection and focusing steps is to
present a sufficient number of ions to the collision surface at a
sufficient rate to allow detection of any photon emissions which
result. If the detecting means chosen is particularly sensitive,
such as single photon counting means, then tolerable collection
efficiency could, of course, in general be lower than required with
less sensitive detection means such as photo diodes, scintillation
devices or proportional counters. The next step of ion acceleration
is critical to the obtaining of the low-energy collision-induced
emissions. The acceleration step must in general produce ions
having energies of at least 3 to 5 electron volts above the energy
arrived at by the following equation:
where
E.sub.s is the threshold energy for the sputtering of surface atoms
in their electronic ground states,
E* is the excitation energy of a specific excited state of the
sputtered atom,
m.sub.1 is the mass of the incident ion or molecule, and
m.sub.2 is the mass of the sputtered atom.
Standard excitation energies E* are known, and are therefore not a
necessary part of this description. They are obtainable, for
example, in energy level tables published by the National Bureau of
Standards. Likewise, threshold energies E.sub.s are known for a
number of ionic species incident on a variety of surfaces, but in
any event are readily determinable by simple experimentation.
The energy of the ion beam may be as large as desired. However, it
will ordinarily be preferred to have a beam energy of from 100 to
4,000 electron volts, below which the signal intensity resulting
from the photon emissions is in general too low to be conveniently
detected, and above which power consumption and probable
destruction of the sample surface outweigh the advantage of
increased signal intensity.
Where the surface to be analyzed exhibits a conductivity value
which is low enough to permit significant charge buildup on the
surface and resultant repulsion of incoming ions, charge buildup
may be avoided by placing a conducting grid on the surface or in
close proximity to it. The distance between the conducting members
of the grid is, of course, not critical, but should be such as to
allow a beam transmission of at least 40 percent and preferably for
optimum signal intensities at least 80 percent. By way of example,
copper grids having 25 lines per centimeter and a transmission of
about 80 percent are commercially available.
The species chosen to collide with the sample surface must do so at
a sufficient energy to sputter excited particles therefrom, and
thus may be of any element except hydrogen, whose mass is in
general insufficient to cause significant sputtering at low
energies due to insufficient momentum transfers. Since at present
it is most convenient to obtain collision particles of the proper
energy by accelerating charged particles through an ion lens, it
will ordinarily be preferred to choose easily ionizable and
relatively stable gases having substantial masses such as nitrogen
and the rare gases, Ne, Ar, Kr, and Xe.
The pressure in the target chamber must be sufficiently low such
that the intensity of photon emissions from sources other than the
sample surface is negligible in comparison to the spectral peaks of
interest. In general, a pressure in the target chamber of
.apprxeq.5.times.10.sup.-.sup.6 Torr or less will be required. This
pressure is readily achieved by diffusion pumping. The beam current
must be sufficient to provide the minimum number of collisions
desired per unit of time and is thus determined by the ion
collection efficiency, the intensity of the photon emissions and
the sensitivity of the detection means. When using single photon
counting techniques the number of collisions per unit of time may
be as low as 10.sup.4 per second.
It will ordinarily be necessary to obtain calibration spectra for
the collision pairs of interest. Such procedure permits the
unequivocal identification of unknown species and their relative
concentrations in a solid sample surface by comparison of their
spectra with the calibration spectra.
Referring now to FIG. 1 there is shown one embodiment of the
inventive apparatus in which ion beam source 10 provides ions,
aperture 11 collects the ions, ion lens 12 accelerates the ions to
the proper energy while also focusing the ions into an ion beam 13
and directing the beam through aperture 14 into collision chamber
15 containing the sample 16 to be analyzed. The sample is
positioned so that at least one surface is bombarded by the ion
beam. Photons emitted as a result of the collisions pass through
quartz window 17 and spectrometer 18 to a photomultiplier tube 19.
The electrical signals produced by the impact of photons on the
photomultiplier tube are conducted through leads 20 to conventional
signal processing equipment not shown where the counting rate is
determined and registered. Chamber 15 may be evacuated through port
21. Due to the fact that photon emissions from the sputtered
particles originate within a continuous space from the sample
surface to some distance away from it, typically 0.01-0.5 cm. at
these energies, the position of the detection equipment is not
critical.
The above-described apparatus is suitable for the obtaining of
calibration spectra and also for obtaining spectra of samples whose
constituents are not predictable. Where the identities of the
constituents are suspected or known, it may be more convenient to
replace the spectrometer with narrow band transmission filters so
as to obtain photon counts for only the spectral regions of
particular interest.
EXAMPLE 1
Using an apparatus similar to that shown in FIG. 1, collisions were
obtained for the 10 pairs and at the ion energy shown in Table I
below, and the resultant photon emissions were detected over the
wavelength ranges indicated.
---------------------------------------------------------------------------
TABLE I
Ion Acceleration Energy (3,000 ev.)
Wavelengths Collision Pair Detected (A.) Pair Number 2800-6600
He.sup.+ and Ni 1 2800-6000 N.sub.2 .sup.+ and Ni 2 2800-7800
Ar.sup.+ and Ni 3 3200-6600 N.sub.2 .sup.+ and Cu 4 3200-6600
Ar.sup.+ and Cu 5 3200-6600 Ne.sup.+ and Cu 6 3200-7800 N.sub.2
.sup.+ and Ge* 7 3200-7800 Ar.sup.+ and Ge* 8 2800-6800 N.sub.2
.sup.+ and Si* 9 2800-6800 Ar.sup.+ and Si* 10
__________________________________________________________________________
Conducting grids were placed over these sample surfaces
Results are depicted graphically as emission spectra in FIG. 2, 3,
4, 5, 6, 7, 8, 9 and 10, respectively, for the pairs listed in the
table. The intensity of photon emissions (arbitrary units) is
plotted versus wavelength (angstroms) in each figure. In FIG. 2 the
intensity peaks at about 3,900, 4,300, 5,900 and 6,570 A are
attributable to sources other than the Ni surface, such as source
radiation and surface contaminants. The remaining peaks including
those at about 3,000, 3,050, 3,100, 3,240, 3,380, 3,390, 3,415,
3,461, 3,519, 3,570 and 3,620 A, are substantially attributable to
Ni. In FIG. 3 the intensity peaks at about 3,900, 4,300 and 5,900 A
are attributable to sources other than the surface. The remaining
peaks including those previously mentioned and also including those
at about 3,680, 4,080, 4,220 and 4,600 A are characteristic of the
nickel surface.
In FIG. 4 is shown the spectrum for pair number 3. The peaks at
about 4,300 A and 6,580 A are attributable to sources other than
the Ni surface, while the remaining peaks including those mentioned
for FIG. 2 and 3 above are generally characteristic of the Ni
surface.
In FIG. 5 is shown the spectrum for pair number 4. The intensity
peaks at about 3,250 A and 3,270 A and their second order
counterparts at about 6,500 A and 6,540 A are attributable to
copper. The peak at 5,000 A is tentatively attributed to copper,
and the remaining peaks are due to other sources.
In FIG. 6 and 7 are shown the spectra for pair numbers 5 and 6. The
four intensity peaks for copper pointed out above for pair number 4
are again evident. Other peaks are attributable to other
sources.
In FIG. 8 and 9 are shown the spectra for pair numbers 7 and 8,
respectively. The intensity peaks at about 7,680 A and 7,700 A are
attributable to germanium. The peaks between 3,200 A and 3,600 A
are tentatively attributed to germanium, while the remaining peaks
are due to other sources.
In FIG. 10 and 11 are shown the spectra for pair numbers 9 and 10,
respectively. The peaks for copper are evident in these spectra,
since a copper grid was placed over the sample surface prior to
bombardment. These peaks occur at about 3,250, 3,275, 6,500 and
6,550 A. The peaks at about 2,880, 4,440, 4,870, 5,015, 5,035,
5,055 and 5,770 A are attributable to silicon. The peaks at about
3,365 A and those from about 5,550 to 5,720 A are tentatively
attributed to silicon. The remaining peaks are due to other
sources.
EXAMPLE 2
Using an apparatus similar to that shown in FIG. 1, collisions were
obtained for an N.sub.2 .sup.+ ion beam on a nickel surface over
the ion acceleration energy range of from about 20 to 3,000
electron volts. The excitation efficiency was measured over the
wavelength range of about 3,365 to about 3,375 A. The excitation
efficiency may be defined as the number of photons emitted per
incident ion. The results are shown in FIG. 12 where excitation
efficiency or cross section is plotted on the vertical scale (in
arbitrary units) against ion acceleration energy. It may be seen
from the figure that excitation efficiency increases abruptly from
a low value at about 50 electron volts and continues to increase
rapidly to about 200 electron volts, beyond which it gradually
decreases as a function of energy. The steep sloped region at about
50 electron volts may be termed the excitation threshold for the
nickel surface and is characteristic thereof. It will thus be
appreciated that determination of the characteristic excitation
threshold presents an additional technique for the identification
of solid surfaces.
The invention has been described in terms of a limited number of
embodiments. Other embodiments are contemplated. For example, since
it is the function of the collision particles simply to produce
sputtered particles of the surface constituents in an excited
state, the ion beam described may be replaced by a beam of neutral
particles provided, of course, these particles collide with the
surface at the requisite energies. In such a case, the problem of
repulsion of the beam by a charged sample surface is in general
substantially avoided.
While the gaseous particles have been described as forming a beam,
it will be appreciated that the particle distribution in the sample
chamber may be such that a "beam" is not differentiable in the
ordinary sense, and yet sufficient collisions be obtained to allow
the practice of the invention.
* * * * *