SURFACE A M ) INTERFACE ANALYSIS, VOL.

24, 431-447 (1996)

Ion-implanted Surface Analysis Reference

Materials: Certification of Dose Densities from
to loi3 cm - 2

Werner H. Gries
Research Centre FTZ, Deutsche Telekom, PO Box 10 00 03,64276 Darmstadt, Germany

This German contribution to the VAMAS prenormative project on ion-implanted reference materials describes a
general procedure for the certification of retained dose densities of elements of the third and higher periods of the
Periodic Table at levels of foremost technological interest, i.e. 1016-1013 cm-’ (i.a atoms cm-’), in wafer-type
host materials. The proposed procedure satisfies all requirements of a definitive method and can be readily imple-
mented in many laboratories worldwide. In a first step, a primary reference material (PRM) at several loi5 cm-2
is certified by referencing to a weighed, evenly spread deposit of the analyte by means of wavelengthdispersive
x-ray fluorescence spectrometry (WDlXFS). All further certification of retained dose densities is relative to this
PRM. Dose densities of similar level are certified (relative to the PRM) by means of WD/XFS or electron
microbeam analysis (also by Rutherford backscattering spectroscopy if Zhpl>Zh,,). Dose densities below loi5
cm-’ are certified (relative to the PRM or a substitute) by means of comparative in situ ion dosimetry. Require-
ments are specified for the deposit, the ion implants, the measurements by WD/XFS and certification by compara-
tive in siiu ion dosimetry. The procedure is verified by experiment.

INTRODUCTION to the latter, it is the quantity of implanted analyte

~ retained at the end of implantation per unit area of ion-
Reference materials and certified reference materials
(CRM) have important functions in the application of
surface analysis techniques. Reference materials can be
considered to consist of two components : the analyte of
interest and a suitable carrier or host. Ion implantation
of the analyte (in the following, also referred to as the
implantant) into the host has become a much-favoured
process for manufacturing reference materials. The
development of recommendations for the manufacture
of reference materials by ion implantation and the certi-
fication thereof to the status of CRM is one of the
VAMAS projects,’-3 which may eventually lead to I S 0
norms. The present situation regarding reference
materials and CRM for secondary ion mass spectrom-
etry (SIMS) was recently reviewed at an international
workshop4 and is exemplary also for other surface
analysis techniques. At the workshop it was concluded
that ion implantation continues to be the method of
choice for the manufacture of reference materials for
surface analysis by SIMS, but that the values claimed
for the dose density (see following paragraph) and for
the concentration us. depth profile of currently available
ion-implanted reference materials lack the reliability
necessary for quantification, and that certification is
required. It was agreed that the most immediate need is
for certification of the dose density.
At this stage attention must be drawn to the fact that
the term ‘dose density’ has a different meaning to
implanter technologists and surface analysts : to the
former (who prefer to use the term ‘dose’ rather than
‘dose density’), the term means the total number of ions
incident per unit surface area during the implantation
process as derived from in situ ion current integration;
CCC 0142-2421/96/070431-17
0 1996 by John Wiley & Sons, Ltd.
exposed surface. Here, the term ‘retained dose density’ is
used for the latter quantity in accordance with earlier
IUPAC recommendations ;7 the term ‘nominal dose
density’ is used to designate the quantity quoted by the
implanter technologist. The relationships between the
retained dose density and other dose density quantities
are clarified in the next section. Wherever the term ‘dose
density’ appears in this paper without specifying adjec-
tive, it stands for retained dose density.
The retained dose density is usually expressed in units
of ‘number of retained atoms per unit area of the ion-
exposed surface’, i.e. m-’ in the mks system. By tradi-
tion, the lo4 times smaller unit of cm-’ is used
worldwide and is used also throughout this paper.
This paper deals with certification of the retained
dose density by means of a ‘definitive method in a tech-
nically valid procedure’ as defined by the I S 0 defini-
tions of 1981/855*6 (see Appendix 1). In Ref. 6 a
definitive method is defined as a method based on a
‘valid, well-described theoretical foundation’ ensuring
‘negligible systematic errors relative to end-user require-
ments’ and providing for the reference property to be
‘related to the basic units of measurement’ (mass, length
and time) ‘through physical theory expressed in exact
mathematical equations’.
Medium- to low-level dose densities of 10i6-10’
cm-’ are in particular demand for quantitative surface
analysis investigations of semiconductor materials. The
difficulty of certification arises from the fact that these
levels cannot be determined by means of direct mass
and area measurement (as would be ideal), and that
existing methods of analysis of sufficient detecting
power lack generality and/or depend themselves on
(generally unavailable) CRM for quantification.
Received 25 J u f y 1995
Accepted 4 March 1996
432 W. H. GRIES
For this reason a method of certification was pro-
posed in 1970,8 which allows an accurate link to be
established between the retained dose density and the in
situ ion current integration in implanters of high mass
resolution, known as ‘quantitative ion implantati~n’.~.’
The method qualifies as a definitive method and was
therefore proposed for use in the VAMAS p r ~ j e c t . ~
Implementation of quantitative ion implantation as a
means of certification of the retained dose density is
becoming ever more difficult, however, by a worldwide
trend away from implanters of high mass resolution
towards high-current machines of low mass resolution.
High-resolution research implanters (and personnel) are
phased out. Another practical problem in the imple-
mentation of quantitative ion implantation arises from
the fact that the surface analyst has to relinquish
control over the certification process to the implanter
technologist. Experience has shown the traceability of
certification to suffer in such conditions. Therefore, the
development of an alternative definitive method for
dose density certification is called for.
The procedure put forward in the present paper is
such an alternative; it satisfies all requirements of a
definitive method, it is widely applicable, certification is
in the hands of the analyst and implanters of low mass
resolution can be made use of. It is essentially a means
of referencing the retained dose density of a given
analyte ion-implanted into a given substrate to a weigh-
able (and hence larger) deposit of the same analyte
spread out evenly on an identical substrate. The mass of
the deposit is determined by weighing. Wavelength-
dispersive x-ray fluorescence spectrometry (WD/XFS) is
then used to determine the unknown quantity of
analyte in the ion-implanted specimen relative to the
known quantity of analyte of the deposit. Values of
dose density (of the implant) and spread density (of the
deposit) are derived from measurements of the related
surface areas. The implant so certified becomes the
primary reference material (PRM) for all further certifi-
cation. The deposit is not used again, as it is vulnerable
to physical handling and chemical attack by environ-
mental gases.
Obviously, this method of certifkation is unsuitable
for the rare gases and for the ultralight elements which
produce little or no x-ray fluorescence. The highly reac-
tive alkalis and gases capable of forming compounds
have to be deposited as compounds. For these elements
and for the rare gases the alternative is quantitative ion
implantation.
Wavelength-dispersive XFS is chosen for referencing
for a variety of reasons. It is a non-invasive method of
analyte excitation of high element specifcity and power
of detection, it is well understood and it is widely used.
Furthermore, the broad-beam nature of the primary
(exciting) x-rays generated by the tube sources in stan-
dard laboratory spectrometers is of cardinal importance
for successful referencing for the following reasons
(further elaborated below). Firstly, the thickness of the
deposit may not exceed a few hundred pg cm-2, imply-
ing that the deposit must be spread over several cm2 for
it to become weighable. Broad-beam radiation is
required to cover the entire deposit. Secondly, most
deposits of this thickness turn out to be non-ideal on a
microscopic or even mesoscopic scale. Broad-beam
radiation is required for averaging over the local non-
uniformities such that a quasi-uniform deposit is simu-
lated. Thirdly, broad-beam radiation keeps the
radiation density at a sufficiently low level for specimen
heating not to become a problem.
A drawback of WD/XFS is that the low limit for
accurate determination of the retained dose density with
standard laboratory WD/XFS spectrometers is at the
1015 levello for chemical elements of the third and
higher periods of the Periodic Table, i.e. one to two
orders of magnitude above the lowest level for which
CRM are required. The implication is that for these ele-
ments one has to accept that the PRM has a dose
density above the 1015cm-’ level.
For the light elements boron to fluorine, the low-dose
density limit is even higher; it increases rather rapidly
towards boron, for which element it is expected to reach
1017 cm-2. These light elements have not been included
in the investigations reported in Ref. 10, whence the
procedure proposed here pertains primarily to elements
of the third and higher periods of the Periodic Table
(except for the rare gases).
For these analytes and retained dose densities below
10’’ cmP2,a certification in two stages is proposed. In
stage 1, a PRM is certified as just proposed (i.e. by WD/
XFS-referencing to a weighed deposit), while in stage 2
the (low) dose density of interest is referenced to that of
the PRM. The proposed method of referencing in stage
2 is the comparison of nominal dose densities, as
obtained by conventional ion implanter dosimetry
under certain conditions specified below.
The paper is subdivided as follows: the essentials of
ion implantation, the related terminology and the
requirements for the two-stage procedure are sum-
marized; then the actual procedure is discussed in
detail. The mathematics for stage 1 certification by XFS
spectrometry is developed next, followed by a quantitat-
ive treatment of the influence of interelement excitation.
Thereafter, the quantities are discussed which determine
the low-dose density limit for accurate determination by
WD/XFS. Next, specifications are derived for the
deposit of analyte for stage 1 certification. Thereafter,
stage 2 certification is dealt with. Finally, stage 1 of the
procedure is experimentally verified.
The guiding principle in developing the certification
procedure proposed here has been that the procedure
should be readily applicable in many laboratories
worldwide, such that the end user of the CRM is not
dependent on a particular provider of services or
equipment.
ESSENTIALS OF ION IMPLANTATION,
RELATED TERMINOLOGY AND
REQUIREMENTS FOR THE TWO-STAGE
PROCEDURE
It is assumed that the reader is familiar with the basic
concept of ion implantation as well as with the fact that
an ion implanter is essentially an oversized mass
spectrometer. The ion beam extracted from the ion
source is practically never monoelemental but usually
contains also ions of other chemical elements. As in a
mass spectrometer, each element in the ion beam is
separated into individual beams of its isotopes. One of
the isotope beams of the element of interest is chosen
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS 433

for implantation. In technological implanters the mass

resolution is rather poor (MIAM c 250) and the chosen
isotope beam is often 'contaminated' with ions of neigh-
bouring isotope^.'.^ Low-energy electrons are trapped
in the beam, and ions of isobaric molecules may also be
present. Moreover, a (usually significant) fraction of the
ion beam is neutralized in charge exchange encounters
with residual gas molecules and proceeds as a beam of
atoms. It should be noted that such atoms are present
in the terminal ion beam even if a so-called neutrals
trap is installed in the implanter. A uniform dose
density is achieved by controlled relative movement of
the ion beam and the host material used as beam target.
I
In most implanters, the target is stationary and the ion chargeproportionalrange
of retained dose denstiis
beam is (electrostatically) scanned across. The nominal dose density cm-2

dose density is derived from current integration of the Figure 1. A schematic display of the relationships between the
ion beam in a detector/coulometer combination and a various dose densities of importance. The symbols denote dose
measurement of the beam-exposed aperture of the densities, with subscript 'a' for analyte, and superscripts 'rec' for
detector. Faraday-cup-type detectors are used as a rule." received, 'bsc' for backscattered, 'imp' for implanted, 'spu' for
The analyst is interested only in the retained dose sputtered, 'ret' for retained and 'crit' for critical. The significance of
the charge-proportional range of retained dose densities is
density of the chosen isotope (the implantant) of the explained in the text. It is important to note that the curve labelled
desired analyte in the host material. For the present dis- 'retained dose density' (also known as implantation collection
cussion the analyst has to be acquainted also with the curve) can be obtained from a plot of WD/XFS signals (ordinate)
relationships of the retained dose density to other dose vs. nominal dose density (abscissa). This plot is the basis for
experimental determination of the critical dose densityd:'".
densities, as well as with the relationship to the in situ
charge density measurement by means of the detector/
coulometer combination mentioned above (Table 1 and
Fig. 1 pertain). The terms used are fully defined in a safe to assume the measurement to yield a nominal
IUPAC re~ommendation.~ charge density rather than the received charge density.
It should be noted that a Faraday cup in a techno- If, moreover, the ion beam is non-ideal (as is common
logical implanter does not necessarily qualify as ideal in in technological implanters), it follows that the dose
the sense used in Table 1. Unless proof is provided that density value quoted by an implanter technologist is
the Faraday cup is in fact a black-hole detector, it is usually a nominal dose density. The latter value is an
important quantity for stage 2 of the procedure.
Turning to the other dose densities shown in Fig. 1,
Table 1. Quantities of charge and implantant incident on the the received dose density refers to the ions and atoms of
target by way of an ion beam the chosen implantant incident on the target surface, the
implanted dose density refers to those coming to rest
Quantity Obtained by
inside the target (while the remainder is backscattered)
Received charge density Beam current integration using and the retained dose density refers to those left in the
qreC(cm-') an ideal' Faraday cup target after implantation (i.e. after a fraction of those
Nominal charge density Beam current integration using implanted has been lost as a result of sputtering).
9""" (cm-') a non-idealb Faraday cup
It should be noted that only if both the beam and the
Nominal dose density Derivation from q""" on Faraday cup qualify as ideal (as defined above) can the
dno" the (unrealistic) assumption of received dose density be derived from the (actually
an ideal' ion beam measured) received charge density. These are two of the
Received dose density Derivation from either qreCon prerequisites for quantitative ion implantation. Further
d'"" (cm-') assumption of an ideal" ion prerequisites are that dbsc and dspu (Fig. 1) should be
beam or d"' +dspu dbgC+ rendered insignificant, such that dre' becomes practically
(see Fig. 1)
Implanted dose density Derivation from either d"" -dbSc
equal to 8"". Then, and only then, the retained dose
d i m P(cm-') (see Fig. 1) or d"' +daPu density can be directly derived from the received charge
(see Fig. 1) density.
Retained dose density Derivation from either The quantity dspu is rendered insignificant if dimp is
d"' (cm-') dreC -dbSC -dSPY (see Fig. 1) or kept below the (so-called) critical dose density Pit(Fig.
post-implantation measurementd 1). The critical dose density is of cardinal importance
'A Faraday cup open to incident ions but closed to incident elec- for stage 2 of the procedure. The quantity dbsc is ren-
trons as well as all secondary emission of charged particles from dered insignificant if the implantant and the host
inside the cup (elsewhere in this paper, also termed a 'black-hole' material are chosen such that Mimpl2 Mhost,where M
Faraday cup). designates the mass number. If Mimpl< &Ihost, the quan-
b A Faraday cup not (completely) closed to secondary emission of
charged particles from inside the cup.
tity dbsccan be rendered insignificant by use of a suffi-
" A beam consisting only of identical ions of the desired isotope. ciently high energy of implantation.
If the beam is non-ideal, a nominal dose density is arrived at by The procedure described in this paper is an improve-
measurement of either a nominal or the received charge density. ment over certification by quantitative ion implantation
dBy the procedure described in this paper or by an alternative because there is no requirement for the chosen beam to
definitive method.
be an ideal beam. Hence, technological implanters of
434 W. H. GRIES
low mass resolution can now also be made use of. This
implies, of course, that not only is the chosen isotope
implanted but also the neighbouring isotopes (if
present), i.e. the implanted elemental analyte is likely to
consist of two or more isotopes at a non-natural abun-
dance ratio.
As stated in the introduction, the low-dose density
limit for WD/XFS certification at stage 1 is ~ 1 0 ' ~
cm-' for elements of the third and higher periods of the
Periodic Table. Retained dose densities below this limit
are certified by comparative in situ ion dosimetry. For
this purpose two implants are required, one at the dose
density of interest (below the limit) and another at a
dose density above the limit (i.e. the PRM or a substi-
tute referred to above). Then, two of the requirements of
quantitative ion implantation have to remain in force :
the quantity dbsc has to be rendered insignificant for
both implants (except when identical hosts are used);
and both implants have to be below the critical dose
density. A third requirement, according to which the
detector should be a black-hole Faraday cup, can be
dispensed with if the detector is separated from the
target and electron suppression is used on the detector.
This is standard in so-called X-Y overscanning
arrangements, where one or more Faraday cups with
electron suppression are placed at the perimeter of the
target. If these conditions are met, d"' is strictly pro-
portional to both q""" and d""" provided that the oper-
ating conditions of the implanter (i.e. the intensity,
composition, energy and focus of the beam, as well as
the residual gas pressure) remain invariant from one
implantation to the next. Then, the retained dose den-
sities below the critical dose density can be termed the
'charge-proportional range of retained dose densities'
(as shown in Figs 1, 2, 3 and 5). It should be noted that
the critical dose density increases with ion energy.
If the retained dose density of interest exceeds the
low-dose density limit of stage 1, then stage 2 and its
conditions are not relevant. Only one implant is
required at the proper dose density, and none of the
four prerequisites of quantitative ion implantation (see
above) need to be met.
OUTLINE OF THE PROCEDURE FOR
CERTIFICATION OF THE RETAINED DOSE
DENSITY OF AN ION-IMPLANTED ANALYTE
The proposed procedure for certification of a retained
dose density below the 1015 cm-' level is shown sche-
matically in Fig. 2. An ion-implanted working reference
material (WRM) is shown at the bottom of the dose
density scale ('spread density' in Fig. 2). The dose
density level (n3 x 1013 crnp2) is too low for stage 1
certification. Hence, it is referenced to the PRM by
means of comparative in situ ion dosimetry (i.e. by
ratioing of the nominal dose densities). The dose density SRM and WRM. Also the TRM has a silicon wafer as
of the PRM (n2 x 1 O I 6 cm-') exceeds the low limit for
stage 1 certification. The PRM is stage 1 certified by
reference to a deposit reference material (DRM) with a
known spread density of analyte that is two orders of
magnitude larger (n, x 10'' cm-'). Stage 2 certification
implies that the PRM and the WRM have to be ion
implanted in the same implanter at invariant operating
conditions.
. WDlXFS
dose density
I
charge ratio
Figure 2. A two-stage procedure for certification of retained dose
densities of ion-implanted analyte below the 10" cm-' level:
DRM, PRM and WRM denote deposit, primary and working refer-
ence materials, respectively. The DRM carries the analyte as an
overlayer, while in the PRM and the WRM the analyte is ion
implanted. The host materials are identical for the DRM and the
PRM. The term 'spread density' is used as a generic term and
includes the dose density for ion implants. Spread density levels
are indicated. The spread density of analyte on the DRM is suffi-
cient for accurate determination by mass (and area) measurement.
The PRM is referenced to the DRM by wavelength-dispersive
x-ray fluorescence spectrometry (WD/XFS). The WRM is refer-
enced to the PRM by conventional implanter dosimetry under
conditions specified in the main text.
The certification procedure sketched in Fig. 2 rep-
resents the simplest case possible. This simple procedure
can yield only a few WRM specimens because of the
requirement that WRM and PRM have to be implanted
in one batch to satisfy the requirement of invariant
operating conditions. The VAMAS concept overcomes
this handicap by the introduction of two further refer-
ence materials with intermediary function. Figure 3
shows this VAMAS-conform procedure.
A major consideration of the VAMAS concept is that
the task of certification is shared between the end user
and a few major suppliers of CRM. The major suppliers
would see to the certification of the PRM, and they
would issue duplicates of the PRM to the end user.2
These duplicates are referenced to the PRM by means
of WD/XFS or electron microbeam analyis (EMA) (also
by RBS if Zimpl> Zhost);they would have the status of
secondary reference materials (SRM). Silicon wafers
would normally be used as analyte carriers for the
DRM, PRM and SRM. The end user is expected to
produce the WRM (or have it produced). The carrier
material for the WRM is provided by the end user (and,
hence, is that which best suits the intended application).
A transfer reference material (TRM) is ion-implanted
together with the WRM, and serves as a link between
carrier material. The certification of the TRM against
the SRM would be undertaken by the end user or by a
service laboratory chosen by the end user, again by
means of WD/XFS or EMA (or RBS). The remainder of
Fig. 3 follows the pattern set by Fig. 2 and is self-
explanatory.
Before certification of implants from an unknown
implanter is embarked upon, the lateral uniformity of
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS 435

N F

+ CRM supplier
w
1
analyst *
Figure 3. A VAMAS-conform two-stage procedure for certification of retained dose densities of ion-implanted analyte below the 10l6
cm-2 level. This is an adaptation of the certification procedure of Fig. 1, in accord with the VAMAS concept of task sharing between a few
major suppliers of certified reference materials (CRM) and the analyst. See the legend to Fig. 1. A secondary and a transfer reference
material have been added (SRM and TRM, respectively);both are ion implanted. The host materials are identical for the DRM, the PRM, the
SRM and the TRM. The SRM is referenced to the PRM by WD/XFS and is issued to the analyst. The WRM is referenced to the TRM by
conventional implanter dosimetry under the conditions specified in the main text. The TRM is referenced to the SRM by WD/XFS.

implantation has to be verified. At the 10” cm-’ level The attenuation correction. For XFS as the method of
and above, electron microbeam analysis can be applied measurement, an expression for the relationship
in the point mode with micrometre lateral resolution. between the quantity of analyte and the measured fluo-
At lower levels, digital image analysis of the lateral dis- rescence intensity for different depth distributions of the
tribution of ion signals obtained by SIMS can provide analyte has been derived b e f ~ r e , ’ ~ ,Equation
’~ 12 in
point-to-point information at a similar lateral Ref. 14 is rewritten here as
resolution.
Q/Qr = (F/Fr) e x ~ ( A-
t A , tr)
Implications of the VAMAS-conform procedure for X
1 + (A,’/2!)tI, (A,3/3!)tI3 + (A,4/4!)tI,
- -* ..
certification by WD/XFS 1 + (A2/2!)t, - (A3/3!)t3 + (A4/4!)t4 - * * *

The VAMAS-conform procedure of Fig. 3 calls for a
total of five reference materials. Four of these have iden-
tical carriers (silicon wafers): DRM, PRM, SRM, TRM.
With the last three, the analyte is buried in the carrier
and the depth distribution is of the ion-implanted (bell-
shaped) type. These depth distributions are different
only for different energies of implantation. This con-
trasts with the DRM, where the analyte is on-surface
and its depth profile is of rectangular shape. The strong-
ly different analyte distributions of the DRM and the
PRM give rise to a significantly different attenuation of
the primary and fluorescent x-rays, which has to be cor-
rected for. This correction is dealt with in the next
section.
Interelement (or secondary) excitation is another pos-
sible cause for correction. Such a correction may
become necessary if the fluorescence x-rays of the
carrier are sufficiently energetic to excite the analyte (in
addition to the primary excitation). For instance, the L
fluorescence of analytes of Z I36 is excited by the K
fluorescence of silicon. The percentage increase of the L
fluorescence as a result of interelement excitation is dif-
ferent for different analyte distributions. Therefore, if the
L fluorescence is to be used for stage 1 certification and
the interelement excitation is of significance, the differ-
ent percentage increases in the signal from the DRM
and the PRM must be corrected for. This correction is
dealt with in a later section.
(1)
where A and A, are ‘attenuation parameters’ given by
A = p, + & cosec $
cosec 4
A , = prpcosec 4 + prfcosec $
Symbols Q denote quantities of analyte, F the measured
fluorescence x-ray intensity obtained therefrom for a
given primary x-ray intensity and subscript r denotes
the specimen regarded as reference. The quantities
denoted by p are mass absorption coefficients (MACs),
where subscripts p and f denote those for primary
x-rays and fluorescence x-rays, respectively. The angles
4 and $ are measured with respect to the surface; they
are the angles of incidence (primary x-rays) and take-off
(fluorescence x-rays), respectively. The quantities
denoted by t are moments of the two depth distribu-
tions of analyte concerned: t and t, are the distribution
means (1st algebraic moments), t , and trZare the ‘devi-
ation’ moments (2nd central moments), t , and t,, are
the ‘skewness’ moments (3rd central moments) and t,
and t,, are the ‘kurtosis’ moments (4th central
moments). Higher moments are not normally required.
It should be noted that the density quotient of Eqn.
12 in Ref. 14 is in error and has been dropped from
Eqn. (1).
Equation (1) is the general form of the attenuation
correction, applicable to different depth distributions
and different mass absorption coefficients, in the
436 W. H. GRIES

absence of interelement excitation. It expresses the

signal-to-quantity relationship between WRM and
TRM, TRM and SRM, and PRM and DRM.
It should be noted that the relationships between the
1st moment and the higher moments can be expressed
by',
t, = k,t" and tm = k,,t,"; n 2 2
where factors k,, and k,, depend on the type of depth
distribution.
For the rectangular analyte distribution of the DRM,
the values of k,, are:13 k,, = 0.33, k,, = 0 and k,, =
0.25. Moreover, t, = 0.5 t , , where t, is the thickness
(here, mass thickness) of the deposited analyte.
For the ion-implanted analyte distribution of the
PRM the values of k,, are not fixed, because the shape of
the depth distribution varies with ion energy as well as
with the atomic numbers of implantant and host
material. The values of k, can be obtained either from
so-called ion-range tables or from Monte Carlo simula-
tions of ion ranges (e.g. by the well-known TRIM code).
In most range tables only the first two moments are
tabu1ated,I6 as so-called projected range R , and the
standard deviation of the projected range AR,, 1.e. ' t=
R, and t , = (ARP)'. Of the two tables in Ref. 16 only Figure 4. Various relationships between fluorescence intensities
that of Smith covers all possible combinations of ( F ) from a given quantity of analyte either deposited on (cases a
(monoelemental) implantant and carrier material. The and e) or in (cases b, c and d) two matrices, one of which (matrix
1st to 3rd moments are tabulated in the two works 2) gives rise to interelement excitation of the analyte." The equa-
tions are for measuring situations where x-ray attenuation is quasi-
quoted in Ref. 17 and the 1st to 4th moments are tabu- linear (primary as well as fluorescence). The depth Pistribution of
lated in Ref. 18. None of the three latter tabulations the buried analyte is represented by its mean depth ( t ) .
covers all possible combinations of implantant and
carrier.
Concerning the 3rd and 4th moments of ion- A delta layer of analyte is considered, positioned at
implanted analyte distributions, it is helpful to note that depth t , in Fig. 4(d), and positioned on the surface in
the 3rd and 4th moment terms in the series in Eqn. (1) Fig. qe). The signals due to direct (primary) excitation
are insignificant for smali values of the product At (i.e. are denoted by F,, and Fop,respectiveiy. These are the
for low ion energy and a small mass absorption signals which would take the place of F and F , in Eqn.
coefficient) and can be dropped from the series. For (1) in the absence of interelement excitation. The signals
most ion-implanted analytes in a silicon wafer the 3rd due to interelement (or matrix) excitation are denoted
and 4th moment terms in the series in Eqn. (1) remain by F,, and F,, ,respectively. The ratio of F,, to F,, is
insignificant for implantation energies at sub-MeV different to that of F,, to FOP,as can be seen from the
levels and for signals of K fluore~cence.'~ For L and M expressions for F,, and F,, . Hence, if the total signals
fluorescence, the 3rd and 4th moment terms may Fzp,,,, , Fop,Om were to be used for F and F , in Eqn.
and
(l),the quantity ratio Q/Q, would be in error. Therefore,
assume values of significance.
the actually measured signal ratio F,,, ,,,,/Fop, has to,,
The interelement excitation correction. Expressions for the be corrected for the change brought about by inter-
increase of the analyte fluorescence signal resulting from element excitation. The interelement-excitation-free
interelement excitation by the fluorescence x-rays ratio F,JF,, is received by use of the expression
emitted from a carrier material were developed in Ref. (derived in Appendix 2)
12. These expressions and the corresponding measuring
situations are shown in Fig. 4 (i.e. Fig. 2 in Ref. 12,
redrawn) and were derived for measuring situations
where a linear approximation to the Lambert-Beer law where apz = ppz cosec 4 and a, = pm2[1+ Ei(pm2tz)l;
of x-ray attenuation is considered to be a good approx- Ei denotes the 'exponential The reader is
imation. Then, a delta layer at the centroid depth can be referred to Ref. 12 for a discussion of the role of the
used as substitute for an ion-implanted analyte distribu- exponential integral. He may also find it helpful to note
tion. +
that if p,,,,t, % 1, the sum 1 Ei(pm2t2)can be written
For the interelement-excitation correction required as cosec 4m,where the value of 4,,, changes from 11.5"
here, parts (d) and (e) of Fig. 4 are of relevance. The to 20.8" as pmztz changes from 0.01 to 0.1." The quan-
notation of Ref. 12 has been retained in Fig. 4, where t' tities denoted by p are again MACs; pp, is the MAC for
denotes the centroid depth. In other equations in this primary x-rays in matrix 2 and pmzis the MAC for fluo-
paper the centroid depth is denoted by bold lettering, rescence x-rays of matrix 2 in matrix 2. Factor k
i.e. t. It should also be noted that the thicknesses t and f denotes the fractional increase of analyte fluorescence
in the equations in Fig. 4, as well as all t, are in units of resulting from secondary excitation from matrix 2 at the
mass thickness (g cm-'). depth position t , of the delta layer of analyte. A value
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS
equal to the centroid depth of the ion-implanted analyte
distribution is to be used for t , .
For Eqn. (2) to be solved, one requires a value for k,
i.e. one has to know what the contribution of the inter-
element excitation is to the total excitation. Predictive
equations exist15 for this contribution to be estimated.
If these predictions show the contribution to be small,
then this prediction will also be sufficiently accurate for
a calculation of the (then small) correction by Eqn. (2).
If the predictions point to a large contribution, the
uncertainty on the predicted value may be unacceptably
large. It would then be necessary to determine the exact
value by experiment. An exact value is readily obtained
if one uses the procedure shown schematically in Fig. 5.
The analyte concerned is ion implanted in both a
wafer of the material giving rise to interelement excita-
tion (e.g. Cr in GaAs) and a wafer of a material not
giving rise to interelement excitation (e.g. Cr in Si). The
energy of implantation must be high enough for back-
scattering to be either at a negligible level or so small
that predictive values are acceptable as a correction. Of
crucial importance is that both implantations are done
in a single implanter at invariant operating conditions,
and that both dose densities are below the respective
critical dose densities as well as above the low-dose
density limits for stage 1 certification. The ratio of the
two dose densities, nl/n2 in Fig. 5, is then identical to
the ratio of the nominal dose densities, and the inter-
element excitation can be derived from this ratio and
the ratio of fluorescence signals in WD/XFS.
By using again the theory and notations of Ref. 12
(Fig. 2, b and d; here, Figs 4(b) and 4(d)), the following
expression has been derived (cf. Appendix 2) for k
where AQ and I F stand for ‘attenuation quotient’ and
‘interelement excitation factor’, respectively, given by
AQij2 = C1 - (up1 + afi)til/Cl - (mp2 + d t 2 1
I F , = 1 + (ap2 a,,)t, + (SIB ratio) scales with the dose density, this ratio was
In analogy to the expressions for CI given above
clPl = ppl cosec 4 established at which a 1% uncertainty on the signal
a,, = pfl cosec
af2 = pf2 cosec * For a signal S on a background B and a statistical
where ppl denotes the MAC for primary x-rays in
matrix 1, pfl the M A C for fluorescence x-rays of analyte
N charge ratio
n, ~ 1 0 ’ 6 c m ~ 2 n, x 1 0 ’ ~ c m ‘ ~
E
. z%!
.-3
C
v)
(u
D mask material, acceptance angle setting of the Soller
I
0
TI
431
in matrix 1 and pfz the MAC for fluorescence x-rays of
analyte in matrix 2.
The lowdose density limit of stage 1 certification
To repeat, the low-dose density limit of stage 1 certifica-
tion is the lowest dose density value at which the x-ray
fluorescence signal received from the ion-implanted
analyte can still be measured with a given small uncer-
tainty. This value primarily depends on the total quan-
tity of analyte exposed to the primary x-rays, the
primary x-ray intensity, the signal-to-background ratio
and the measuring time. For a given measuring time the
primary x-ray intensity and the signal-to-background
ratio depend primarily on the source of x-rays, so much
so that the low-dose density limit in a standard tube-
sourced WD/XFS spectrometer is typically at the
cmP2 level,” whereas in an optimized synchrotron-
sourced WD/XFS spectrometer it is predicted to be at
the l O I 3 cm-2 level.” These dose density values depend
on the surface area exposed to the primary x-rays (it is
the total quantity of analyte which counts). For a given
area of exposure and a given uncertainty, the low-dose
density limit assumes a lower (and, hence, better) value
for a shallow implant than for a deep implant.
In this paper we are concerned with tube-sourced
WD/XFS spectrometers, an area of exposure from 5 to
10 cm2 and an uncertainty of 1%for all quantities con-
tributing to the dose density limit. The analyte is
assumed to be shallow implanted. The low-dose density
limit is determined for these conditions and for a mea-
suring time of 2000 s.
The low-dose density limits pertaining to these condi-
tions were derived from experimental data for DRM, i.e.
for spread densities of surface-deposited analyte about
three orders of magnitude larger than the low-dose
density limits. Because the signal-to-background ratio
used as the basis of calculation of the latter from the
former. For this purpose, the SIB ratio limit had to be
would not be exceeded. This SIB ratio limit is now
derived.
error of 1% on S, we have
J(S + B) = 0.01s or S = 104(1+ B/S) (4)
Equation (4) provides the relationship between S and
S/B for a 1% statistical error on S. It tells us that the
value of S must be a minimum of lo4 counts if S 9 B. It
also tells us that if the S/B ratio decreases, then the
value of S must increase for Eqn. (4) to remain valid.
E .g For a given measuring time and invariant primary
x-ray intensity, the signal decreases in proportion to the
gg
nu decreasing quantity of analyte. Under the same condi-
tions and with identical hardware (carrier material,
slc collimator), the background is invariant. Hence, also the
S/B ratio decreases in proportion to the decreasing
quantity of analyte. The increase of S required to offset
this effect can only be brought about by an over-
proportional increase of measuring time. The maximum
measuring time allowed is 2000 s and the SIB ratio
438 W.H. GRIES
which corresponds to this measuring time is now calcu-
lated. This is our S/B ratio limit.
The aim must be to maximize the total count ( S + B)
within the allowed measuring time. There is an upper
limit, set by the maximum count rate that can be
handled by the detector, and there is an alternative
upper limit, set by the highest primary x-ray intensity
deliverable by the source. The maximum total count
( S + B) is determined by the lower of these two limits.
The limit set by the detector is determined by the
dead time of the photon detector. Flow-proportional
counters as used in WD/XFS spectrometers can handle
count rates of 5 x lo5 s-l for dead time errors of 1%.
Multiplication by a measuring time of 2000 s yields a
maximum of 1 x lo9 counts for S + B. Substitution in
Eqn. (4)leads to S/B = 0.003.
In a tube-sourced WDJXFS spectrometer, the
primary x-ray intensity is such that the background
does not normally exceed a value two orders of magni-
tude less, i.e. about 5000 s-’. Multiplication by a mea-
suring time of 2000 s yields a maximum of l x lo7
counts for B. Substitution in Eqn. (4) leads to S /
B = 0.03. This, then, is the SIB ratio limit that one can
go to in stage 1 certification under the constraints of
boundary conditions as specified above. This SIB ratio
limit determines the low-dose density limit for a tube-
sourced WD/XFS spectrometer.
From rhodium-tube-sourced WD/XFS measurements
on 15 analytes (ranging from Mg to Au) deposited on
four different substrates (Si, SiO,, GaAs, InP), it has
been deduced” that the low-dose density limit for stage
1 certification is generally close to the 1015cm-’ level if
the analysed area is between 5 and 10 cm2 and the
above boundary conditions are applied. To quote two
values from Ref. 10 for the carrier material silicon:
1.6 x 10” cm-’ for Ka fluorescence from the analyte
Mg and 0.7 x 1015 cm-’ for La fluorescence from the
analyte Au. This level was verified by several measure-
ments on ion-implanted specimens. As an example, in a
later section on experimental verification the measure-
ment on a 6.7 x 1014 cm-2 implant of As in Si is
reported, which was undertaken at an SIB ratio of 0.05.
At an SIB ratio that low, it is of the utmost impor-
tance to know the exact spectral shape of the back-
ground beneath the signal. This has to be determined
on an identical unimplanted material. Of equal impor-
tance is the choice of the spectrum positions left and
right of the signal from the implanted carrier, where
substitute measurements of the background are to be
made.
THE DEPOSIT REFERENCE MATERIAL FOR
STAGE 1 CERTIFICATION: SPECIFICATIONS
AND SOURCES OF UNCERTAINTIES
The first consideration is that the x-ray fluorescence
intensity is proportional to the quantity of analyte
exposed to the primary x-rays and that, hence, a suffi-
ciently large surface area of the PRM must be exposed
for the low-dose density limit of stage 1 certification to
be brought down to the cm-’ level. The area
required is 2 5 cm’.
The second consideration is that the analyte spread
out on the DRM must be exposed to an identical radi-
ation to that of the PRM for the fluorescence intensities
to be proportional to the quantities of analyte.
A third consideration is that in standard WD/XFS
spectrometers the specimen exposure to the exciting
x-rays is highly non-uniform. To compensate for this
non-uniform exposure, at least to some extent, speci-
mens are rotated in these spectrometers at -0.5 revol-
utions s-l, which ensures that all analyte atoms at the
same radial distance from the centre of rotation are
exposed to the same radiation (on time average). The
effect is the same as if the radiation were non-uniform
only in the radial direction.
The second and third considerations combined
require the analyte spread area on the DRM to be iden-
tical to that of the exposed area of the PRM, not only
in size but also in shape and position. Furthermore,
within the area defined for the deposit, the analyte must
be uniformly distributed. For WDJXFS spectrometers
with specimen rotation, these requirements can be
relaxed to read: ‘to the fluorescence detector, the
analyte on the DRM must appear to be distributed
identical to that in the PRM in size, shape and position;
also, the analyte must appear to be uniformly distrib-
uted‘.
The relaxation of the requirement of strict uniformity
of the deposit to one of apparent uniformity is of deci-
sive importance, because (as stated already in the
introduction) most deposits of suitable thickness turn
out to be non-ideal on a microscopic or even meso-
scopic scale. Specimen rotation will cause this non-
uniformity to appear evened out to the detector.
Specimen rotation ensures that apparent shapes are
either circular areas or annular areas concentric to the
axis of rotation, depending on the radial extent of the
analyte deposit. For practical reasons, to be explained
in an instant, the real shape chosen for the analyte
deposit on the DRM is that defined by the intercept of a
broad annulus and a sector with a sharp apex angle (Fig.
6). By adjusting the apex angle, the thickness of the
deposit can then be tailored to satisfy four boundary
conditions for the deposit: a lower and an upper limit
on the mass, and a lower and an upper limit on the
thickness.
The lower limit on the mass derives from the require-
ment that the analyte should be weighable to an uncer-
tainty not exceeding f 1%. The upper limit on the
mass derives from the requirement that the PRM and
DRM must be measured with identical spectrometer
settings, and that the fluorescence intensity must not
exceed a value where detector dead-time correction
causes a quantification error in excess of 1%. The lower
limit on the thickness derives from the requirement that
the native oxide layer forming on the deposit in the time
interval between first exposure to air and weighing must
not exceed 1%. The upper limit on the thickness derives
from the requirement that x-ray attenuation in the
deposit must not assume values where the uncertainty
on the mass absorption coefficients used in Eqn. (1)
would cause the uncertainty on the corrected signal to
exceed f1%. Actual values corresponding to these
boundary conditions are quoted below, but first we
return to Fig. 6.
As stated above, the analyte on the DRM must
appear to the detector to be uniformly spread over the
area defined for the deposit. In other words, in the case
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS
\deposit
Figure6. Shape and position of the deposit of analyte on a
carrier wafer for use as a deposit reference material in stage 1 certi-
fication: (a) on a whole wafer (not recommended); and (b) as
recommended; (c) mask for measurement.
of a non-ideal deposit the (microscopic or mesoscopic)
non-uniformities must be spread evenly across the
deposit area. Because the averaging occurs in the direc-
tion of specimen rotation and not radially, it is of par-
ticular importance that the dimension of the deposit in
the rotational direction is not too small for the averag-
ing to become effective. This is the first of two reasons
for choosing the deposit shape as shown in Fig. 6(b)
rather than a sector shape as in Fig. 6(a). The other
reason is that it is rather difficult in practice to achieve
a uniform deposition at the apex of a sector-shaped
deposition mask. This then explains the shape chosen
for the analyte deposit on the DRM.
For the actual referencing of the PRM to the DRM,
both specimens are identically masked as shown in Fig.
-
qc). Results reported later were obtained" with masks
exposing 7 cm2 of surface area.
Now, the four boundary conditions on the analyte
deposit are returned to. The lower limit on the mass of
the deposited analyte is 200 pg for an uncertainty
margin of Gl'Xo. This figure has been derived" from
weighing tests performed on a mechanical microbalance
and two electronic ultramicrobalances of well-known
make. The reproducibility was found to be not better
than f2 pg for any one of the three balances.
The upper limit on the mass of the deposited analyte
has been tied to the dead-time correction of the detec-
439
tor. If experimental datalo are compared to detector
specifications given in the previous section (where count
rates of 5 x lo5 s-' for dead-time errors of 1% are
claimed for flow-proportional counters), this upper limit
would be at the 5 mg level. In general, this limit will be
found to be too large if the attenuation uncertainties are
also considered (see below).
The lower limit on the thickness is 50 pg cmP2if the
deposit is an ideal thin film (and the analyte is of
medium mass number). This figure is based on the well-
known fact that the mass gain due to formation of a
native oxide layer is typically at the level of 0.5 pg cm-2
and on the assumption that a full native oxide layer has
formed by the time the analyte deposit is weighed. In
general, the deposit is not an ideal thin film and this
lower limit may have to be raised by a factor of 1.5-3,
depending on the topography and coherence of the
deposit. Two examples of a non-ideal deposit are con-
sidered here : columnar growth (slow surface diffusion
during deposition) and island growth (fast surface diffu-
sion during deposition).
In the case of columnar growth, the deposit has the
appearance of a rough-surfaced coherent thin film. This
film consists of more or less tightly packed individual
vertical columns. For a day after deposition, oxida-
tion of the rough surface proceeds at about the rate for
a smooth surface; the mass gain is larger by a factor
equal to the ratio of the real surface area to the geomet-
ric surface area. After the fast superficial oxidation,
oxygen may proceed also into the intercolumnar spaces,
leading to an oxide skin formation down the column
sides. The rate of intercolumnar oxidation is oxygen-
diffusion-controlled, and hence is slow. Depending on
the column diameters, the oxide oxygen can eventually
amount to a significant percentage of the deposited
analyte mass. This may have to be taken into consider-
ation if an aged DRM is to be used for stage 1 certifica-
tion.
The situation is more complicated if the deposit con-
sists of a distribution of islands. In that case, it is recom-
mended that the coverage of the substrate by these
islands be determined (e.g. by image processing), as well
as their height distribution (e.g. by optical interference
techniques). The capping of the islands by native oxide
can be derived from these data and the oxidative mass
gain can be estimated therefrom to good approximation
(to check for compliance with the 1% uncertainty rule).
Lastly, the upper limit on the thickness is discussed,
which is imposed by attenuation uncertainties. It is
based on the fact that for K fluorescence of medium-to-
high-2 analytes the MAC is usually known to not
better than +5%. Hence, if a fraction r of the excited
fluorescence is absorbed in the deposit, this excited fluo-
rescence is uncertain to +5r%, where the fractional
loss itself is given by r = 1 - exp( - pt), where p is the
MAC and t is the thickness of the deposit. The effect of
a thickness variation on the uncertainty of the excited
fluorescence is shown in Table 2 for uncertainties of 5,
10 and 20% of the MAC.
For example, for p = lo00 f 100 cm2 g-', the uncer-
tainty of the excited fluorescence can be kept at -t 1% if
the thickness of the deposit does not exceed 100 pg
cm-2. For medium-to-high-2 analytes, the MAC for
self-absorption (i.e. absorption of analyte fluorescence in
the analyte itself) is significantly smaller than loo0 cm2
440 W.H. GRIES
Table 2. Percentage uncertainty of the excited fluorescence for
given absorber thickness t as a result of an uncertainty
on the mass absorption coeffcient p of 5,lO and 20%
P r +5r(%) * 1or(./.) *2(*(%)
0.1 0.095 0.5 1.o 1.9
0.2 0.18 0.9 1.8 3.6
0.3 0.26 1.3 2.6 5.2
0.4 0.33 1.6 3.3 6.6
0.5 0.39 2.0 3.9 7.8
g-’. Hence, the upper limit on the thickness is pro-
portionately larger for these analytes. An uncertainty
margin of + 5 % instead of 10% of the MAC allows
the thickness to be doubled.
The MAC of the primary x-rays is always smaller,
usually significantly smaller, than that of the fluores-
cence. Therefore, the upper limit of the deposit thickness
is dominated by the uncertainty of the fluorescence
attenuation.
In conclusion, an analyte deposit of thickness
between 50 and several hundred pg cm-’ and total
mass a200 pg can be recommended for the DRM for
stage 1 certification.
STAGE 2 CERTIFICATION
As explained above, there are two prerequisites for stage
2 certification : a sufficiently high critical dose density;
and a strict proportionality between the retained dose
density and the nominal dose density below the critical
dose density. The critical dose density constitutes a
high-dose density limit at the upper end of the charge-
proportional range of retained dose densities. A low-
dose density limit does not seem to exist, but is
nevertheless imposed by practical considerations. Both
limits are dealt with in detail in the next section.
A further subject discussed further below is the effect
that a different backscattering of implantant from the
different carrier materials of the WRM and the TRM
has on stage 2 certification. This topic is dealt with in a
later section.
The low- and highdose density limits of stage 2
certification
The low-dose density limit is quickly explained. It
derives from the requirements that: the operating condi-
tions of the ion implanter have to remain invariant
during the implantation of the two dose densities (low
and high); and the lateral implantant distribution has to
be uniform for either dose density. For the latter
requirement to be satisfied it has been suggestedz6 that
a minimum of 100 identical scan patterns is needed,
which would take about 15 s of implantation time (the
uniformity to be expected from different implanters has
been discussed in Ref. 27). The former requirement
implies that the dose density can be varied only by
varying the time length of implantation. Practical con-
siderations limit this time length to a few hours at most.
Therefore, the low-dose density limit of stage 2 certifica-
tion is three orders of magnitude below the low-dose
density limit of stage 1 certification, i.e. at the lo1’
cm-’ level at its lowest. In practice, one would aim at a
level of 10l6 cm-’ for the TRM and, thus, obtain a low
limit of 1013cm-’ for the WRM.
The critical dose density (i.e. the high dose density
limit) is now dealt with in detail. First, it must be
pointed out that a systematic experimental determi-
nation of the critical dose density has never been
attempted, and that the values available have been
obtained by cal~ulation.~*’~ The calculation is based on
the definition for the critical dose density as that
implanted dose density (i.e. the dose density of implan-
tant trapped in the carrier, regardless of later removal
by sputtering) at which the fractional loss of an implan-
tant due to sputtering of the carrier reaches 1% or, dif-
ferently expressed, at which the retained dose density
drops to 99% of the implanted dose density. Similar cal-
culations have been made for a retention of 95%. These
calculations provide a reasonable to good estimate of
the critical dose density for a wide range of implantant/
carrier combinations and implantation energies. The
predicted values will tell what the implantation energy
should be to ensure that the dose density chosen for the
TRM is safely below the critical dose density. If,
however, the chosen dose density is not safely below but
close to the predicted critical value, the latter must be
checked by experiment. Both, the calculations and the
experimental checking are dealt with below. At the end
of this section, experimental data are made available
which confirm the virtual identity between retained
dose density and implanted dose density at values
below the critical dose density.
Critical dose densities calculated p r e v i o ~ s l yfor
~~~~
implantant/host combinations for which Zimplb Zhost
are shown in Figs 7(a) and 7(b) for implantation ener-
gies of 10, 20, 50, 100, 200 and 300 keV. These were
calculated for implantant depth distributions of two
limiting shapes: a truncated Gauss and a truncated
Cauchy. These proxy distributions were introduced for
lack of a more definite knowledge about the actual
profile shapes. (The Cauchy distribution is also known
as Lorentz or Breit-Wigner distribution. Both the
Gauss and Cauchy distributions are limiting cases of
the family of Student’s t-distributions.) The Gauss and
Cauchy distributions are truncated at the host surface.
The sputtering yields, which are also required for calcu-
lation of the critical dose densities, were obtained from
an experiment-based modification” of the Sigmund
eq~ation.’~
Inspection of Figs 7(a) and 7(b) shows that a threefold
increase of implantation energy leads to a two- to four-
fold increase of critical dose density. A Gauss type of
depth distribution gives rise to a roughly threefold
higher critical dose density than the Cauchy type of
depth distribution.
New critical dose densities have been calculated for
depth profiles simulated by the Monte Carlo code
TRIM.” The TRIM simulation provides a closer
approximation to the actual depth profile than either of
the two limiting distributions (truncated Gauss and
truncated Cauchy). The TRIM-code-based critical dose
densities are calculated for all ratios of Zimp,to Zhost;
values for silicon as host material are shown in Fig. 8
and values for gold as host material are shown in Fig. 9.
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS 441

2, Zl

Atomic number of implantant

ZI 2,

Atomic number of implantant

Figure 7. Normalized critical dose densities for 99% retention of implantants of atomic number Z, in host materials of atomic number
Z, <Z,at six different implantant energies (as parameters) and for two different depth distributions of the implantant: truncated Gauss (a)
and truncated Cauchy (b). The graphs are adaptations from Refs 20 and 7. Actual values of the critical dose density are obtained by
mukiptying the normalized values by the sublimation enthalpy of the host material concerned.

The data of Fig. 8 lie between the corresponding data
for a Gauss and a Cauchy depth distribution in Fig. 7.
This is confirmation for the data in Fig. 7. Only limited
comparison is possible between the data of Fig. 9 and
Fig. 7: with 2, = 2, = 80 in Fig. 7. For these data the
agreement is best for a Gauss depth distribution.
For silicon as a host material, the critical dose den-
sities for 95% retention are seen to be 1.3-2.5 times
higher than those for 99% retention. For gold as host
material, the corresponding factors are close to 3
throughout.
The normalized data in Fig. 8 must be multiplied by
the sublimation enthalpy of 4.7 eV atom-' for silicon in
order for actual critical dose densities to be obtained.
These are seen to be indeed at levels 1OI6 cm-' for all
implantants for implantation energies 210 keV. In
analogy, the normalized data in Fig. 9 must be multi-
plied by the sublimation enthalpy of 3.8 eV atom-' for
gold in order for actual critical dose densities to be
obtained. These are seen to be lowest for high atomic
numbers of both the implantant and the host material.
At least 300 keV ion energy is required to keep the criti-
cal dose density of Bi (say) in Au from falling below
10'' cm-'. The situation is more favourable if the
implantant or the host material, or both, are of lower
atomic number.
For the light elements boron to fluorine, the critical
dose density is seen to increase rapidly towards boron,
for which element it reaches 6 x 10l6 cm-' at 10 keV
and 4 x 1019 cm-' at 300 keV in the host material
silicon. For the host material gold, the corresponding
values are 1.5 x loi6 cm-' and 5 x cm-'. The
implication is that the certification procedure proposed
here for elements of the third and higher periods of the
Periodic Table should be applicable also to the light
elements boron to fluorine, provided that the low-dose
density limit for stage 1 certification stays below the
corresponding critical dose density. Available data on
442 W. H. GRIES

I l a IRu

10
'

I o2

10'

I 10 I - 10
1 o-z
I 0' 0 30 60 II
0 30 60 90
Atomic number o f i m p l a n t o n t
Atomic number o f l m p l a n l a n t
10'
10'
m
10'

I0
'

10'

10'
10'

10'
100

10' 10-

I0
' 30
0 30 60 90
Atomic number o f l m p l a n t o n t
Figure 8. Normalizedcritical dose densities for 99% retention (a)
and 95% retention (b) of implantants of atomic number from 3 to
83 in silicon at four different implantant energies (as parameters)
for depth distributions as simulated by the Monte Carlo code
TRIM.'' Actual values of the critical dose density are obtained by
multiplying the normalized values by the sublimation enthalpy for
silicon (i.e. 4.7 eV atom-').
10'
60 90
Atomic number o f i m p l a n t o n t
Figure 9. Normalized critical dose densities for 99% retention (a)
and 95% retention (b) of implantants of atomic number from 3 to
83 in gold at four different implantant energies (as parameters) for
depth distributions as simulated by the Monte Carlo code TRIM.''
Actual values of the critical dose density are obtained by multi-
plying the normalized values by the sublimation enthalpy for gold
(i.e. 3.8 eV atom-'). It should be noted that the retention values of
99% and 95% are with respect to the implanted dose density, and
thus are exclusive of the (rather large) backscattered fraction.

fluorescence yields3' and MACs suggest that for excita-
tion by rhodium L x-rays the low-dose density limit for
stage 1 certification of fluorine should be at the loi6
cm-' level, for carbon at the 1017 cm-' level and for
boron at several loi7 cm-'. In other words, condi-
tions for certification are favourable for dose densities
upwards from cm-' for fluorine and upwards from
several 1014 cm-' for boron. These projections will
have to be verified in forthcoming experiments. One
may wish to exclude boron from the list, because a
CRM of 50 keV lo1' cm-' "B in a silicon wafer
became available at the US National Institute of Stan-
dards and Technology in 1993.31The dose density was
certified by nuclear reaction analysis.
The critical dose densities shown in Figs 7-9 are reli-
able only if the depth profile used for the prediction is
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS
close to the real implantant profile and the sputtering
yields are realistic. Experimental sputtering yields are
known to sometimes show a significant departure from
the predicted values. The effect on the critical dose
density is of the same significance, because the critical
dose density is inversely proportional to the sputtering
yield. Differences between the assumed and the real pro-
files may result from broadening of the real profile by
radiation-stimulated diffusion or ballistic displacement
of the deposited implantant. Radiation-stimulated diffu-
sion is not quantifiable at present; its effect on the criti-
cal dose density can be estimated from the values
calculated for the Gauss and Cauchy profiles in Fig. 7.
For purposes of Certification, the predictive values of
the critical dose density may have to be confirmed
experimentally. Depth profiling by SIMS can provide a
check on the closeness between the real implantant
profile and the depth profile used for the prediction.
This information is sufficient if implantation is not to be
taken right up to the critical dose density, but only to
(say) half of this value. The sputtering yields used for the
data in Figs 7-9 are not expected to be in error by more
than a factor of two.
If a direct check on the critical dose density is
required, it is recommended that the retained dose
density curve in Fig. 1 be established in the vicinity of
the expected critical value. Absolute retained dose den-
sities are not required, but only analytical signals pro-
portional thereto (WD/XFS, EMA or RBS if Zimp,>
Z
J,., For instance, a plot of WD/XFS signals
(ordinate) us. nominal dose density (abscissa) is con-
structed from a total of four or five well-spaced experi-
mental points which cover the expected critical region
of the curve. In other words, four or five implants are
required for reconstruction of the implantation collec-
tion curve in the region of the critical dose density. In
this approach, the nominal dose density has to serve as
an approximation to the received dose density; the criti-
cal dose density is derived therefrom with due regard to
backscattering (Fig. 1). This procedure has been
appliedg for the implantants 31P and 35Cl in the host
material Al.
Finally, experimental data are referred which
confirm the virtual identity between retained dose
density and implanted dose density at values below the
critical dose density. These data were obtained from
measurements made on the implantants 85Krand 13’Cs
in the host material Al. The implantants are long-lived
radionuclides with well-known half-lives. They were
implanted at 40 and 60 keV, respectively, under condi-
tions prescribed for quantitative ion i.e.
the implanted dose density equals the received dose
density. The retained dose (i.e. the area integral of the
retained dose density) was derived from measurements
of the radioactive decay rate, and the corresponding
received dose from the received charge. In all cases, the
retained dose agreed with the received dose to within
the error margin of f l % to *1.5%. By implication,
the error margin equals the maximum deviation
Table 3. Percentage retention of 40 keV 85Krin Al
Retained dose density (1Oi4 cm-’) 1 .O
Retention (%) (*1.5) 99.5
443
between the retained dose and the implanted dose.
Because the very early results of Ref. 8 (”Kr in Al) are
not readily accessible, they are re-stated here in Table
3.
Effect of implantant backscattering on stage 2
certification
If (as expected) the carrier materials of the WRM and
the TRM differ, it is likely that implantant backscatter-
ing from the two materials is also different. In other
words, the implanted dose density differs for a given
received dose density. Hence, also the retained dose
density differs and stage 2 certification carries a system-
atic error equal to this difference. As stated above, this
error is generally small to negligible for implantant/host
combinations for which the mass number ratio
MimpJMhost 2 1, because then the backscattering itself is
small to negligible.7,9For other relationships the error
can be minimized by raising the implantation energy to
a level where backscattering does become negligible.
What are these energy values?
The most readily available sources of quantitative
information on implantant backscattering are the
graphs published by Eckstein and Biersack” for data
derived by use of the Monte Carlo code TRIMSP.
Individual cases can be investigated directly by use of
one of the various TRIM codes in circulation. Experi-
mental data on backscattering are not so readily avail-
able; most of these confirm the TRIM data. Even so, for
purposes of certification, experimental verification
should be sought for uncertain cases. It is suggested
that this verification be obtained from a measurement
of the implantant depth profile by SIMS. For this
purpose, the pre-equilibrium part of the SIMS profile is
truncated off and the remainder is extrapolated outside
the surface on assumption of either a Gauss or Cauchy
type of profile shape (as for an infinite host material).
The fractional value of this fictitious profile tail pro-
vides a reasonable approximation to the real back-
scattered fraction of the implantant. Particularly for
small fractional values, this procedure is bound to give
more accurate results than any other direct determi-
nation .
Some data on implantant backscattering is provided
in Tables 4-6. Percentage values of implantant back-
scattering from the carriers silicon and gold are given in
Tables 4 and 5, respectively (obtained by use of a TRIM
code”).
Backscattering is indeed seen to be small to negligible
for mass number ratios MimpJMhost > 1. For ratios
below unity, backscattering may be significant
(depending on the ion energy). For a gold target, the
backscattered fraction of most implantants below 300
keV is seen to be too large for referencing the WRM
against the TRM by means of the stage 2 procedure.
The problem is overcome by an appropriate increase of
implantation energy. In Table 6, minimum energies of
1.2 2.2 2.8 5.2 5.3 13
99.4 99.9 99.2 99.0 99.6 99.4
444 W. H. GRIES

spectrometer. The spectrometer used was fitted with a

Table 4. Percentage of normally incident implantant back- rhodium x-ray tube. This led to the appearance of a
scattered from a silicon target for 10,30, 100 and 300 2nd-order diffraction peak of the Rh Ly line near the As
keV ions Ka line of the analyte, giving rise to a non-linear back-
E .OAr and ground. The exact shape of the background was deter-
(keV) 'Li "B 'N' l0Ne "Al higherZ
mined on an As-free silicon wafer of (100) orientation.
10 3.4 2.6 1.9 1.2 0.5 tO.1 Close to 250 pg of As was vapour-deposited on a
30 1.2 1 .o 0.9 0.5 0.2 <0.1 mask-defined area of a wafer of (111) silicon for use as a
100 0.3 0.3 0.3 0.2 co.1 <0.1 DRM. The deposit turned out to consist of randomly
300 <0.1 tO.l <0.1 <0.1 tO.l t0.1 distributed small islands of average height 0.1 pm. The
rotation-averaged spread density of the deposit was
found to be slightly non-uniform in the radial direction,
Table 5. Percentage of normally incident implantant back- requiring a small correction to be applied. Corrections
scattered from a gold target for 10, 30, 100 and 300 for oxidation and interelement excitation (of the As L
keV ions fluorescence) were found to be negligible. Two dose
E
density values in good agreement were obtained by use
(kW 'Li 2541 TO saNb iaiPr ( 0 7 ~ "
of the Ka and La lines of As: (6.74 k 0.54) x 1014cm-'
10 36 29 18 12 6.2 2.4 and (6.54 f 0.46) x 1014 cm-2, respectively. The rather
30 26 25 16 10 5.0 1.9 high uncertainty of 8% is due to the (for stage 1
100 12 19 12 7.3 3.6 1.2 certification) very low dose density; it is bound to be
300 3.4 11 8.6 5.2 2.4 0.8 significantly better for higher dose densities.
Some time after these results were made available to
the organizers of the round robin, the average of 11
Table 6. Minimum implantant energies Eminat which back- individual round-robin results was made known to this
scattering is below 3% (according to data of Ref. 25) author. These round-robin results were obtained by
means of SIMS and the use of relative sensitivity factors
Em,, ( k W for (Mhw,Z,,,,)
I
(RSFs). The RSFs were (reportedly) obtained from
Mlrn.llMhc..*t (200, 80) (140, 60) (100. 44)
%6*
uncertified ion-implanted reference materials available
1 0.004 10 6 3 at the participants' laboratories. At the time of pub-
0.5 0.65 600 300 150 lication of this paper it was not known to this author
0.3 2 900 450 220 how many of these reference materials had been sub-
0.2 3 800 400 200
jected to post-implantation measurement of the retained
0.1 4 450 250 110
dose density and how these data compared to the
a The well-known dimensionless energy of Lindhard, Scharff and nominal dose density. Regardless thereof, one would
Schiott,",'* defined by expect the two dose densities to be close to one another
ELSS { ~ ~ . ~ / [ Z I Z ~ J (+Z?3)l}CMJ(M1
Z:'~ + M2)IE
where E is the energy (in keV) and subscripts 1 and 2 stand for the for the following reasons: an As' ion beam can be pro-
implantant and the host, respectively. duced quasi-pure, except for the fraction of neutralized
ions and a general mass-spectral background. The neu-
trals fraction is expected not to exceed 5% in most pro-
various implantants are given at which backscattering is duction implanters and is likely to be partially or
below 3% (according to data in Ref. 25). completely off-set by the general background. Back-
It is seen that the values in Table 6 fall within the scattering of 100 keV As from Si is negligible (see Table
energy ranges of commercial ion implanters (if MeV 4). Sputter loss of implanted As is negligible at the
implanters are included). Therefore, stage 2 certification above dose density [see Fig. 8(a)]. Hence, any discrep-
can be undertaken even if the carrier material of the ancy between the retained dose density and the nominal
WRM is of highest mass number. dose density arises mainly from use of a non-ideal
Faraday cup. Such a discrepancy is bound to decrease
for the average of 11 individual results.
EXPERIMENTAL VERIFICATION OF STAGE 1 Hence, the average value, given2' as (6.8 & 0.7)
OF THE PROCEDURE ON AN ION IMPLANT x 1014 cm-', is expected to be rather close to the
OF As IN Si retained dose density, even if derived entirely from
nominal dose densities. This value is practically equal
Both stages 1 and 2 of the certification procedure have to the value obtained by use of Ka fluorescence under
been experimentally tested, stage 2 long ago as part of the present procedure, and is within 4% of the value
investigations on quantitative ion irnplantati~n,~-'and obtained by use of La fluorescence. In conclusion, the
stage 1 very recently. Full details of the experimental stage 1 procedure can be regarded as experimentally
testing of stage 1 certification are to be published in a verified.
forthcoming paper." Here, the results are given and
compared to results of a US round robin in duplicate
implants. SUMMARY AND CONCLUSION
These results were obtained on a silicon (100) wafer
ion-implanted with arsenic at 100 keV to a dose density The VAMAS prenormative project on ion-implanted
stated (by the organizers of the round robin) to be a few reference materials is to lead to procedures for the certi-
times 1014 cm-'. This dose density is at the low limit fication of two reference properties of the implanted
for stage 1 certification by WD/XFS in a tube-sourced analyte: the retained dose density and the depth dis-
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS
tribution. The present paper provides experiment-tested
recommendations for the certification of retained dose
densities from 10l6 to 1013 cm-’ (i.e. at all levels of
technological interest) for elements of the third and
higher periods of the Periodic Table.
The recommended procedure has been shown to
satisfy all requirements of a definitive method, while
relying on state-of-the-art standard equipment as avail-
able in many laboratories worldwide. A primary refer-
ence material (PRM) at several 1015 cm-’ is certified
by referencing to a weighed, evenly spread deposit of
the analyte by means of WD/XFS. All further certifica-
tion of retained dose densities is relative to this PRM.
Dose densities of similar level are certified (relative to
the PRM) by means of WD/XFS or EMA (also RBS if
Zimpl> Zhost).Dose densities below 1015cm-’ are certi-
fied (relative to the PRM or a substitute) by means of
comparative in situ ion dosimetry.
Specifications have been developed for the deposit,
concerning size, shape and position on the carrier wafer
(shown in Fig. 6(b)), as well as mass and thickness. The
requirements are that the mass is to be in excess of 200
pg (for measurement by a microbalance), and the thick-
ness is to be between 50 and a few hundred pg cm-’.
These boundary conditions are set to ensure that the
uncertainties arising from weighing, superficial oxida-
tion and correction for signal attenuation are not in
excess of 1% of any of the three.
A VAMAS-conform certification procedure has been
proposed, as shown schematically in Fig. 3. The low-
dose density limit for stage 1 certification by tube-
cm-’ if the analysed area is -
sourced WD/XFS has been reported to be about 1015
5 cm2 and counting
times of half an hour are accepted per individual mea-
surement.
Equation (1) expresses the relationship between
analyte quantities and fluorescence signals for reference
materials with different depth distributions of the
analyte (implanted or as an overlayer). Equation (2) cor-
rects for interelement excitation.
It has been reported that in stage 2, retained dose
densities can be certified at levels within three orders of
magnitude below the low-dose density limit of stage 1,
i.e. in general down to 1013 cm-’ and in favourable
cases down to lo1’ cm-’. Two prerequisites for stage 2
certification are that the retention of implantant is com-
plete (i.e. sputtered losses of implantant are negligible)
and that strict proportionality exists between the
retained dose density and the nominal dose density.
APPENDIX 1
IS0 definitions of reference material and certified refer-
ence material and some critical comments
The following definitions are taken from the 1981
edition of I S 0 Guide 30?
I S 0 dejinition of reference material (RM): a material or
substance one or more properties of which are suffi-
ciently well established to be used for the calibration
445
Concerning the proportionality between the retained
and nominal dose densities, it has been pointed out that
one prerequisite is that the operating conditions of the
ion implanter have to remain invariant during the suc-
cessive implantation of the working and the transfer ref-
erence materials. Furthermore, the Faraday cup used
for in situ dosimetry should be a ‘black-hole’ detector
(i.e. no secondary emission from the Faraday cup),
except when the Faraday cup is separate from the
target, such as in X-Y overscanning arrangements.
The proportionality between the retained and
nominal dose densities is affected if the backscattering
of implantant from the host is significant and different
for the WRM and the TRM. In that case, the energy of
implantation must be chosen sufficientlyhigh for back-
scattering to become negligible. Selected minimum
energy values are provided for guidance (Table 6). Back-
scattering of implantant is not of concern if the host
materials are either identical or of a mass number not
exceeding that of the implantant.
A critical dose density has been defined, below which
complete retention of an implantant is ensured. Nor-
malized values of this critical dose density have been
provided in the form of graphs (Figs 7-9; Fig. 7 based
on an analytical approximation to the depth distribu-
tion, and Figs 8 and 9 on simulation by the TRIM
code). The critical dose density serves also as an upper
limit for the proportionality range of retained and
nominal dose densities.
Experimental data have been reported in verification
of stage 1 of the procedure. Stage 2 has been verified
experimentally during earlier investigations on quanti-
tative ion implantation.
It has been pointed out that the procedure as pro-
posed here for elements of the third and higher period
of the Periodic Table should in principle be applicable
also to the elements boron to fluorine, but only for
drastically larger low-dose density limits (upwards from
1013 cm-’ for fluorine to upwards from several 1014
cm-’ for boron in stage 2).
Acknowledgements
The prenormative work reported in this paper was undertaken at and
funded by the Deutsche Telekom AG (formerly the Deutsche Bundes-
post Telekom) as a German contribution to the international
VAMAS collaboration. T h e data in Figs 8 and 9, as well as the
figures, were kindly generated by S. Krell.
of an apparatus, the assessment of a measurement
method or for assigning values to materials;
I S 0 dejinition of certified reference material (CRM): a
reference material one or more of whose property
values are certified by a technically valid procedure,
accompanied by or traceable to a certificate or other
documentation which is issued by a certifying body.
These definitions have been revised in 1992 ( I S 0 Guide
30-1992). The revised definitions require the property
446 W. H. GRIES
value of a reference material to be ‘sufficiently homoge-
neous’, which can be understood to exclude (the highly
non-homogeneous) ion-implanted RM and CRM. Fur-
thermore, the ‘technically valid procedure’ in the defini-
tion of a CRM has been replaced by a ‘procedure which
establishes its traceability to an accurate realization of
the unit in which the property values are expressed’.
These revisions are not considered to be particularly
helpful in planning a strategy for certification of ion-
implanted RM. This author has, therefore, decided to
continue using the 1981 version.
Even so, while the 1981 definitions are clear on the
use of and the distinction between RM and CRM, the
technically valid procedure in the definition of a CRM
requires further specification. I S 0 Guide 35‘ quotes
three examples from a wider (but unspecified) choice of
technically valid procedures:
(1) measurement by a single dejnitiue method in a single
laboratory;
(2) measurement by two or more independent reference
methods in one laboratory;
(3) measurement by a network of qualified laboratories
using one or more methods of demonstrated accu-
racy.
These examples leave us with three more concepts
requiring clarification.
Only the dejnitiue method is further specified in I S 0
Guide 35:‘ as a method of ‘high scientific status’ based
on a ‘valid, well-described theoretical foundation’ ensur-
ing ‘negligible systematic errors relative to end-user
requirements’. A further requirement is that the pro-
perty in question is to be either ‘measured directly in
APPENDIX 2
Interelement excitation in WD/XFS: derivation of eqns
(2) and (3)
Equation (2) is derived from the relationships given in
Figs 4(d) and 4(e). These relationships pertain to delta
layers of identical quantities of the analyte. Because Eqn
(2) is to be used for different quantities of analyte, these
are assumed here to be nd (crn-’) for the situation in
Fig. 4(d) and n, for the situation in Fig. 4(e). The impli-
cation is that Fopin Fig. 4(d) (denoted by FOp-4d)is no
longer identical to Fopin Fig. 4(e) (denoted by FOp-4,).
In fact, Fop- 4d/FOp- 4, = nd/ne.
First, the ratios F2p/FOp-4e and F2,JFom are com-
pared, and it is found that
F Z m I F o m = C1 + ( a p ~+ am2)t2lF2p/Fop-4e (A2.1)
Then the measured signal ratio is developed as follows
=r (nF 2 p
F~p,~mlF~p,O + FZm)/(F0p-4e + F03
= (F2p/FOm + F~m/f’om)/(Fop- 4e/Fom + 1)
Substitution from Eqn (A2.1) and substitution of F,, by
k Fop- 4 e , followed by simplification and rearrangement,
leads to
FZp, 2m F2p (1 + kC1 + (apZ + am&2I}
-
Om FOp-4e (1 + k)
terms of basic units of measurements’ or ‘related to the
base units through physical or chemical theory
expressed in exact mathematical equations’.
The term reference method has acquired its current
meaning at NIST (National Institute of Standards and
Technology, USA): as a relatively reliable method
which falls short of the full requirements of a definitive
method.24 The handicap of a possibly significant uncer-
tainty associated with a measurement by a reference
method is supposed to be overcome by the use of two
or more independent reference methods, on the implicit
assumption that the results would cluster around the
true value (or ‘value of the measurand’ as it is also
called). The problem associated with any method of
measurement is that the true value cannot be known a
priori, and that, at best, a most probable reference value
can be obtained by means of a definitive method.
Hence, the accuracy ranking of a reference method can
be determined only relative to a definitive method, and
the elevation of a method to the status of a reference
method implies the existence of and comparison with a
definitive method.
The term method of demonstrated accuracy is appar-
ently meant to be self-explanatory, but it raises the
question as to its rankings relative to a definitive
method and a reference method. This author prefers to
regard the term as generic rather than specific. In other
words, a method of demonstrated accuracy can be
either a definitive method or a reference method (having
a specified uncertainty relative to an accepted reference
value as determined by a definitive method in a similar
measuring situation).
and further to Eqn (2).
Of particular interest is that Eqn (2) is independent of
the quantities of analyte involved in the situations in
Figs 4(d) and 4(e). It should be remembered, though,
that Eqn (2) is strictly valid for delta layers only.
Equation (3) is derived from the relationships given in
Figs 4(b) and 4(d). As before, these relationships pertain
to delta layers of identical quantities of the analyte.
Also Eqn (3) is to be used for different quantities of
analyte; these are assumed here to be nb (crn-’) for the
situation in Fig. 4(b) and nd for the situation in Fig. 4(d).
The implication is that FOPin Fig. 4(b) (denoted by
Fop-4b) is no longer identical to Fop in Fig. 4(d)
(denoted by Fop-&,). In fact, FOp-4b/FOp-4d = nb/nd.
The ansatz for derivation of Eqn (3) is
Substitution of F2, by k F2, [l + (ap2+ am2)t2]leads
to
‘2p, 2,JFlp (1 + kC1 + ( a p 2 + a m 2 P 2 I } ( F 2 p / F 1 p )
=
Further substitution of F,, by [l - (ap2
+ a&I and of Flp by El - (apl + afl)fll,and
replacement of Fop- 4d/Fop- 4 b by nd/nb, followed by
rearrangement, leads to Eqn (3), i.e.
k = - 11/IF2
[(Fzp, zm/F~p)(nb/nd)AQzj~
 ION-IMPLANTED SURFACE ANALYSIS REFERENCE MATERIALS
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