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Mass Spectroscopy of Recoiled Ions shorter distance.

By properly adjusting the reflectron


potentials and experimental geometry, all ions of
Mass spectroscopy of recoiled ions (MSRI) is one of a given mass are forced to arrive at the detector
three complementary techniques that comprise time- simultaneously, enhancing the resolution. The use of a
of-flight ion scattering and recoil spectroscopy (ToF– time-refocusing analyzer to improve the resolution of
ISARS). The three ToF–ISARS techniques—ion DR spectra is referred to as MSRI. MSRI is capable
scattering spectroscopy (ISS), direct recoil spectro- of both isotopic resolution for the entire mass range
scopy (DRS), and MSRI—utilize pulsed energetic (including hydrogen, deuterium, and helium) and
primary ions with energies of 5 keV to 15 keV to induce better than part per million (ppm) sensitivity.
a binary collision with the surface (Krauss et al. 1995, High-energy sputtered particles are detected using
Hammond et al. 1995). At these high energies, the the three ToF–ISARS techniques. It has been demon-
collision kinematics are essentially those of classical strated that high-energy particles can travel through
two-body elastic collisions. The energetics of the short, high-pressure, path lengths if the experimental
binary collision induces complete decomposition of apparatus is properly configured (e.g., differential
the molecular species present on the surface. pumping apertures are placed on the end of the
The three techniques differ in the type of analyzer primary ion beam column and the entrance to the
used and the geometry (placement) of the analyzer. In detectors, and these regions are pumped differentially).
ISS, the primary ion strikes the surface at near normal All three ToF–ISARS techniques are capable of
incidence and the backscattered primary ions are surface analysis at high ( 3 mtorr) ambient
detected. The energy of the backscattered ions is pressures (as will be shown below) and can be used for
indicative of the mass of the surface species. ISS is a real-time, in situ analysis and control of thin-film
well-established surface analytical technique that has growth processes (Lin et al. 1994, Im et al. 1996,
been used to study the composition and structure of Smentkowski et al. 1997).
many materials. The sampling depth of ISS is only one
to two layers; ISS is therefore the most surface-
sensitive analytical technique available, and is often
used to determine film growth mechanisms. A limi- 1. Experimental
tation of ISS is that one can only detect elements
heavier than the primary ion. Figure 1 shows a typical ultrahigh vacuum system
For both DRS and MSRI the pulsed ion beam configured for ToF–ISARS analysis (Krauss et al.
strikes the surface at grazing incidence. The binary 1998, Smentkowski et al. 1999). This system utilizes
collision results in the direct ejection of the surface a pulsed Atomika noble gas gun (10 keV Ar+). The
species in the forward scattering direction. DRS pulsed ion beam current is less than 1 nA, which
and\or MSRI analyzers are positioned at grazing exit corresponds to the arrival of " 10* ions sV". The
angles (θr). The kinetic energy of the recoiled species MSRI reflectron analyzer is mounted at a forward
(Er) is given by: scattering angle (θr) of 60 degrees. The hole in the
MSRI pumping aperture\extractor is 1.0 mm in di-
ameter, and the aperture is positioned 44 mm from the
4EoMoMr cos #θr sample. Differentially pumped ISS and DRS detectors,
Er l (1) as well as a Kaufman ion source and a multitarget
(MoTMr)#
carousel for thin film deposition, are present on the
chamber.
where Mo and Mr are the masses of the primary ion The reflectron analyzer used for MSRI contains six
and the surface atoms, respectively, Eo is the energy of main parts: an ion extractor\pumping aperture; lens
the primary ion, and θr is the exit angle. The values assembly; high-voltage, field-free drift region; re-
obtained from Eqn. (1) are only valid for an ideal flectron stack; ion detector; and a neutral (line-of-
binary collision. Deviations from ideal conditions (i.e., sight) DRS detector (Smentkowski et al. 1999). For
multiple collisions) result in the loss of energy, and as positive-ion analysis, large (up to 15 kV) negative
a result each mass has a kinetic energy spread and not potentials are applied to the extractor, the lens, and
a unique single value. The energy spread results in the the field-free drift region. The back ring potential is
broadening of the DRS features towards longer flight positive. For negative-ion analysis the potentials are
times and limits the mass resolution obtained using inverted. Neutral species are not affected by the
DRS. The spread in kinetic energy of the recoiled ions potentials used in the reflectron analyzer and shoot
can be accounted for by diverting the ion fraction into straight through to the line-of-sight detector. The
a reflectron, or time-refocusing analyzer (Sment- reflectron used for MSRI analysis can also be used
kowski et al. 1999). For ions of a given mass, the for time-of-flight secondary ion mass spectrometry
higher kinetic energy ions travel far into the reflectron (ToF–SIMS) analysis when positioned at a suitable
before being turned around, while the less energetic geometry (large θr) (see below). For ToF–SIMS analy-
ions do not penetrate as deep and therefore travel a sis, the potentials applied to the reflectron analyzer are

1
Mass Spectroscopy of Recoiled Ions

Neutral detector pressures up to " 3 mtorr. At high ambient pressures,


the loss in signal intensity is a function of both the
ambient gas pressure and the high-pressure path length
MSRI reflection traveled by the ion beam (" 25 cm). The product of
analyzer
these two quantities, " 75 mtorr cm, provides an
upper limit for MSRI analysis. If the high-pressure
path length could be reduced to 1 cm, surface analysis
could be performed at pressures up to 75 mtorr. At
DRS detector high ambient pressures, only the peak intensities are
attenuated. There is no change in peak position or
lineshape as the pressure increases. Similar effects
Detector are observed for ISS and DRS at high ambient
Differential pressures.
pumping The top panel of Fig. 3 shows a DR spectrum of a
apertures dirty germanium sample. Hydrogen, carbon, nitrogen,
Target carousel Kaufman oxygen, and germanium are easily detected. However,
ion source species present in trace amounts such as beryllium,
sodium, aluminum, chromium, and iron are buried in
the long tails of the dominant species. The lower panel
Substrate of Fig. 3 shows a positive-ion MSRI spectrum col-
lected simultaneously. Elements such as beryllium,
aluminum, chromium, and iron are easily identified.
ISS detector
The spectra shown in Fig. 3 demonstrate the enhanced
resolution and sensitivity of MSRI over DRS.

2.2 Real-time, In Situ ToF–ISARS Analysis of


Thin-film Deposition
Telefocus The top panel of Fig. 4 shows a positive-ion MSRI
ion source spectrum of a dirty platinum sample obtained at a
xenon ambient pressure of 2.2i10V% torr. The middle
panel shows a real-time, in situ MSRI spectrum of the
Figure 1 same sample during sputter deposition (e.g., with the
Typical ToF–ISARS experimental UHV chamber. This Kaufman ion source on). The deposition time, prior to
system was optimized for real-time, in situ, film growth starting the 20 s MSRI data collection, was 30 s. For
studies at high ambient pressures. this set of experiments, a target was not placed on the
stainless steel target holder, and chromium and iron
optimized for low-energy ion detection (Smentkowski were sputter-deposited on to the sample. The lower
et al. 1997, 1999). panel of Fig. 4 shows a MSRI spectrum of the sputter-
For a 10 keV argon primary ion beam and a MSRI deposited film at an ambient pressure of 2.2i
detector position of 60m the recoil energy distribution 10V% torr after turning off the Kaufman ion source;
for the entire mass range, calculated from Eqn. (1), is the total deposition time was 60 s. The MSRI spectra
0–2.5 keV. measured with the Kaufman ion source on (middle
panel) and off (bottom panel) reveal similar trends,
indicating that despite the increase in the background
2. Applications level when the ion source is on, meaningful surface
analysis can be performed. These real-time, in situ
2.1 Surface Analysis at High Ambient Pressure
MSRI spectra reveal an interesting finding. The middle
Figure 2 shows MSRI spectra obtained from a dirty and lower spectra indicate a significant amount of
platinum sample as a function of oxygen pressure. molybdenum on the substrate. The grid on the
These spectra were obtained using 20-second data Kaufman ion source was made of molybdenum. These
acquisition times. At high ambient pressures MSRI spectra show that if the grids are not properly
(2.7mtorr), the pressure in the MSRI housing is aligned, and\or if the source is not running under the
4.8i10V( torr—about three orders of magnitude proper conditions, contamination of the film with the
lower. As the oxygen pressure increases, the signal grid material may occur.
intensity decreases. MSRI spectra, characteristic of The ToF–ISARS techniques are now being used in
the surface composition, were obtained for signal-to- a number of research laboratories for real-time in situ
noise ratios greater than three at ambient oxygen studies of complex multicomponent oxide thin films

2
Mass Spectroscopy of Recoiled Ions

distance and the bond angles for specific species within


the first few atomic layers. The sharpness of the onset
of detection of an underlying species is related to the
surface disorder; well-ordered surfaces show a sharp
increase while disordered surfaces show a gradual
change. Therefore, in addition to the surface com-
position, AR–MSRI also provides information re-
garding the local surface structure.
MSRI intensity

2.3 Surface Phase Identification by MSRI


Although this article focuses on positive-ion MSRI
spectra, one can also measure the negative-ion MSRI
spectra by inverting the polarities on the reflectron
analyzer. It has been demonstrated that the ratio of the
positive ion to negative ion MSRI yields are charac-
teristic of the chemical phase at the surface. Clear
distinctions have been measured for: (i) the hexagonal
and cubic forms of boron nitride; (ii) the different
forms of carbon (e.g., graphite, diamond, and
amorphous carbon); and (iii) the perovskite and
pyrochlore phases of PZT as shown in Table 1.
Monitoring the surface composition and phase during
deposition via the positive-to-negative ion MSRI ratio
Time of flight (ns) provides a simple, inexpensive diagnostic that can be
used to evaluate the properties of the growth surface.
Figure 2 It also provides information that is needed to adjust
MSRI spectra of a dirty platinum sample as a function of the film growth conditions in order to produce
oxygen ambient pressure. selectively a desired surface phase. This type of
information (coupled with process control) would
such as Pb(Zr VxTix)O (PZT), SrBi Ta O (SBT), allow for unprecedented success in the growth of films
Ba . Sr . TiO "(BST), $and YBa Cu #O V#x *(YBCO) that can be only be produced, with high quality, in a
! & ! &et al.
(Krauss $ 1998). MSRI is also
# $ being
( used to narrow range of growth conditions.
monitor GaN thin film growth in situ and in real time
(Kim et al. 1997, 1999). It has been shown that the
Ga+\N+ MSRI ion ratio is indicative of the film
2.4 Comparison of MSRI and SIMS
quality. Comparison of the Ga+\N+ ion ratio
measured in situ via MSRI with ex situ photo- It is important to note the difference between SIMS
luminescence spectra shows clear trends. Good films and MSRI. The hardware used for MSRI is similar to
have a MSRI Ga+\N+ ion ratio of 3.0 and a photo- that used for ToF–SIMS (Benninghoven 1994). For
luminescence full width at half maximum (FWHM) of MSRI, the geometry is chosen to emphasize single
40 meV, whereas bad films have a MSRI Ga+\N+ ion collision ejection events rather than the multiple
ratio of 9.0 and a photoluminescence FWHM of collision cascade mechanism associated with the SIMS
219 meV. Angle-resolved mass spectroscopy of re- process. Both the kinetic energy and the ion fraction of
coiled ion (AR–MSRI) studies of GaN are now being the ejected surface atoms are much higher for MSRI
performed during thin film deposition. This is done by than for SIMS. In SIMS, the atoms are ejected close to
keeping both the angle of incidence of the primary ion the sample normal as a result of a cascade of numerous
beam (αr) and angle of detection (θr) constant and small-angle collisions between the recoiling target
rotating the sample azimuthally. Plots showing the atoms (i.e., collision cascade), rather than between the
locus of trajectories of primary ions reveal regions primary ion and the target atom. By the time a surface
behind each surface target atom where the primary ion atom receives enough momentum from the cascade to
beam is excluded (referred to as the shadow cone). be ejected normally from the surface, the kinetic energy
Atoms in the shadow cone are not sampled by the has degraded to only a few electronvolts. The sputtered
primary ions and do not contribute to the MSRI species leave the surface with only a few electronvolts
signal. As the azimuthal angle changes, atoms pre- of energy, regardless of the primary ion energy. The
viously located in the shadow cone may become low-energy SIMS atoms ejected from the surface have
visible. The angle(s) where underlying species become a significant amount of time during which charge
visible can be related quantitatively to the bond exchange can occur between the surface and the

3
Mass Spectroscopy of Recoiled Ions

DRS intensity (counts)

Time of flight (ns)


MSRI intensity(i105 counts)

Counts
Time of flight (ns)

Figure 3
Simultaneously collected DR (top) and MSRI (bottom)
spectra of a dirty germanium sample showing the
enhanced resolution and sensitivity of MSRI. These data
were collected using a 10 keV potassium ion beam and θ l
15m and 72m for DRS and MSRI, respectively.

Time of flight (ns)


departing atoms, resulting in a high degree of charge
neutralization of the sputtered atoms. The amount of
Figure 4
charge neutralization changes drastically as the surface
MSRI spectra of platinum: at 2.2i10V% torr of Xe (top),
composition changes. In SIMS, the ion fraction is low during sputter deposition (middle), and after deposition
(typically only 10V#–10V&); as the composition of the (bottom).
surface changes, the ion yield can vary by up to five
orders of magnitude. This is the well-known SIMS
‘‘matrix effect’’ (Benninghoven 1994). In contrast to Table 1
SIMS, the sputtered species in DRS–MSRI leave the Positive ion to negative ion MSRI ratio.
surface with much greater energies (see Eqn. (1)), and Sample Element jIon\kIon
are less prone to charge neutralization with the surface.
As a result, the ion fraction of the direct recoil atoms Hydrocarbon C 3.0
often exceeds 10% and in many cases approaches Graphite C 1.0
Diamond C 0.5
100%. In contrast to MSRI, both elemental species Hexagonal BN B 20
and molecular fragments are detected in SIMS. How- Cubic BN B 12
ever, the SIM spectra can be difficult to interpret. PZT (pyrochlore) Zr 150
If the reflectron analyzer is positioned at a large Pb 12
forward scattering angle (large θr), it is possible to PZT (perovskite) Zr 32
obtain pure MSRI or pure SIM spectra. Although Pb 5
MSRI analysis is possible at high ambient pressures,
SIMS is not—due to the low velocity of the sput-
tered SIMS species. Figure 5 shows a positive-ion could be made between MSRI and SIM spectra
SIM spectrum of a dirty germanium sample. The SIM obtained from the same sample. For SIMS analysis,
spectrum was obtained immediately after the MSRI the sample was rotated in such a way that the sample
spectrum shown in Fig. 3 so that a direct comparison normal was close to the center line of the reflectron

4
Mass Spectroscopy of Recoiled Ions

3. Summary
It has been shown that MSRI (as well as the other
ToF–ISARS techniques) can be used for real-time, in
situ film growth studies at high ambient pressures.
Surface analysis via MSRI has a number of ad-
vantages. First, it has the ability to monitor all surface
species with isotopic resolution and high sensitivity in
a quantitative fashion. Second, the ratio of the positive
ion to negative ion MSRI yields are indicative of the
surface phase and can be used as a process control
diagnostic. Third, it is able to perform surface analysis
at high ambient pressures, and if installed at a suitable
geometry, the reflectron analyzer used for MSRI can
Time of flight (ns) also be used for ToF–SIMS. MSRI provides quan-
titative elemental analysis while SIMS provides clues
Figure 5 as to the molecular species present on the surface.
Positive-ion SIM spectrum of a dirty germanium sample. MSRI and SIMS provide complementary information
The SIM spectrum was obtained immediately after the that cannot be obtained by either technique alone. The
MSRI spectrum shown in Fig. 3. use of AR–MSRI to measure the local surface struc-
ture in situ and in real time represents an exciting new
area of research.

analyzer, and the voltage applied to the back ring of


the reflectron analyzer was lowered from 1500 V (for
MSRI) to 50 V (for SIMS). The obvious difference
between the MSRI and SIM spectra is the lack of 4. Acknowledgments
molecular ions and molecular fragments in the MSRI The author would like to thank A. R. Krauss, and
spectrum, making the positive identification of deu- D. M. Gruen (of Argonne National Laboratory) as
terium, nitrogen, aluminum, chromium, and iron well as J. Albert Schultz, J. C. Holecek, and K. Waters
straightforward. Elemental ions as well as molecular (Ionwerks) for assistance and support during the
fragments are detected in the SIM spectrum. In the postdoctoral appointment during which the work
SIM spectrum, one cannot distinguish deuterium from reported above was performed.
H ; additionally, CxHy fragments prevent the positive
#
identification of nitrogen (vs. CH ), oxygen (vs. CH ),
aluminum (vs. C H ), chromium #(vs. C H ), and iron % See also: Secondary Ion Mass Spectroscopy; Auger
# $ % %
(vs. C H ). Since the beryllium feature measured using Electron Spectroscopy; Chemical Analysis, Electron
MSRI% and) SIMS cannot be attributed to any other Spectroscopy; Depth Profiling; On-line Measurement;
species, a comparison of the beryllium MSRI and Rutherford Backscattering Spectroscopy; Focused
SIMS yields can be used to estimate the sensitivity of Ion Beam Characterization Techniques
these two techniques. The observation that similar
beryllium yields are obtained using both techniques
indicates that the sensitivity for MSRI is comparable
with that for SIMS. The resolution (peak FWHM) is
similar for both MSRI and SIMS for peaks with only Bibliography
one component. For peaks with multiple components Benninghoven A 1994 Surface analysis by secondary ion mass
in the SIM spectrum (i.e., 14 amu; N and\or CH ) the spectrometry (SIMS). Surf. Sci. 299/300, 246–60
resolution decreases. # Hammond M S, Schultz J A, Krauss A R 1995 Surface analysis
The spectra shown in Figs. 3 and 5 illustrate that at low to ultrahigh vacuum by ion scattering and direct recoil
MSRI and SIMS provide complimentary information. spectroscopy. J. Vac. Sci. Technol. A 13 (3), 1136–43
In MSRI only elemental ions are detected, whereas Im J, Krauss A R, Lin Y, Schultz J A, Auciello O H, Gruen
D M, Chang R P H 1996 In situ analysis of thin film
elemental ions and molecular ions are detected in
deposition process using time of flight (ToF) ion beam analysis
SIMS. SIMS therefore provides clues as the molecular methods. Nucl. Instrum. Methods Phys. Res. B 118, 772–81
species present on the surface. Since the MSRI ions Kim E, Bensaoula A, Rusakova I, Schultz A, Waters K 1997
leave the surface with a large kinetic energy, they are ToF–LEIS characterization and growth of GaN thin films
not as susceptible as SIMS ions to charge neutra- grown with ECR and NH . Mater. Res. Soc. Symp. Proc. 449,
lization with the surface. In MSRI, the ion yield varies $
318–24
by less than a factor of ten as the chemical state of the Kim E, Berishev I, Bensaoula A, Rusakova I, Waters K, Schultz
surface changes, simplifying quantitative analysis. J A 1999 ToF mass spectroscopy of recoiled ion studies of

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Mass Spectroscopy of Recoiled Ions

surface kinetics and growth peculiarities during gas source Smentkowski V S, Holecek J C, Schultz J A, Krauss A R, Gruen
molecular beam epitaxy of GaN. J. Appl. Phys. 85, 1178–85 D M 1997 Surface analysis of all elements with isotopic
Krauss A R, Auciello O, Schultz J A 1995 Time of flight, ion- resolution at high ambient pressures using ion spectroscopic
beam surface analysis for in situ characterization of thin-film techniques. In: Gillen G, Lareau R, Bennett J, Stevie F
growth processes. MRS Bull. 20 (5), 18–23 (eds.) Secondary Ion Mass Spectrometry, SIMS XI. Wiley,
Krauss A R, Im J, Smentkowski V S, Schultz J A, Auciello O, New York, pp. 1083–86
Gruen D M, Holecek J, Chang R P H 1998 Ion beam Smentkowski V S, Krauss A R, Gruen D M, Holecek J C,
deposition and surface characterization of thin multi-com- Schultz J A 1999 A novel reflectron time-of-flight analyzer for
ponent oxide films during growth. Mater. Sci. Eng. A 253, surface analysis using secondary ion mass spectroscopy and
221–3 mass spectroscopy of recoiled ions. J. Vac. Sci. Technol. A
Lin Y, Krauss A R, Chang R P H, Auciello O, Gruen D M, 17(5), 2634–41
Schultz J A 1994 Atmosphere influence on in situ ion beam
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Copyright ' 2001 Elsevier Science Ltd.


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Encyclopedia of Materials : Science and Technology
ISBN: 0-08-0431526
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