Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578

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Characterization of the effects of soft X-ray irradiation on polymers
1
*
T. Coffey, S.G. Urquhart , H. Ade
Department of Physics, North Carolina State University, Raleigh, NC 27695, USA
Received 4 December 2000; accepted 23 July 2001
Abstract
The physical and chemical effects of the soft X-ray irradiation of polymers have been systematically evaluated for photon
energies just above the C 1s binding energy. This exposure causes radiation damage in the form of the loss of mass and
changes to the chemical structure of the polymers. These effects are evident in the Near Edge X-ray Absorption Fine
Structure (NEXAFS) spectra of the exposed polymers, posing a fundamental limit to the sensitivity of NEXAFS
spectroscopy for chemical microanalysis. Quantitative understanding of the chemistry and kinetics of radiation damage in
polymers is necessary for the successful and validated application of NEXAFS microscopy. This paper outlines a method for
quantifying this radiation damage as a function of X-ray dose, and applies these methods to characterize the loss of mass and
loss of carbonyl group functionality from a diverse series of polymers. A series of simple correlations are proposed to
rationalize the observed radiation damage propensities on the basis of the polymer chemical structure. In addition, NEXAFS
spectra of irradiated and virgin polymers are used to provide a rst-order identication of the radiation chemistry. 2002
Elsevier Science B.V. All rights reserved.
Keywords: NEXAFS spectroscopy; Polymers; Damage; Quantitative; Analysis; Radiation chemistry
1. Introduction from X-ray or electron spectroscopy necessarily
causes radiation damage to the exposed material.
Near Edge X-ray Absorption Fine Structure Polymers in particular are sensitive to radiation
(NEXAFS) spectroscopy, performed with high spa- damage caused by X-ray and electron irradiation
tial resolution in X-ray microscopy, is a powerful [711]. The particular risk for spectroscopic micro-
method for the microchemical characterization of analysis is that the sample and its spectrum might
polymer materials [14]. Like its cousin, Electron degrade faster than meaningful microanalysis can be
Energy Loss Spectroscopy in Transmission Electron performed. For chemically meaningful microanaly-
Microscopy (e.g. TEM-EELS) [5,6], the combination sis, it is therefore critical to understand both the form
of high spatial resolution with chemical sensitivity and the rate of the soft X-ray radiation damage. With
a quantitative understanding of the radiation damage
kinetics, it can be possible to design experiments that
*Corresponding author. Tel.: 11-919-515-1331; fax: 11-919-
work within a tolerable damage limit. Currently, the
515-7331.
level of radiation damage for X-ray microscopy of
E-mail address: harald ade@ncsu.edu (H. Ade).
]
1
polymers is not so severe as to prohibit the analysis
Present address: Department of Chemistry, University of Saskat-
chewan, Saskatoon, SK S7N 5C9 Canada. of most polymer materials [4,11]. However, the
0368-2048/ 02/ $ see front matter 2002 Elsevier Science B.V. All rights reserved.
PI I : S0368- 2048( 01) 00342- 5
66 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
inevitable push to higher spatial resolution and the
elucidation of more subtle spectroscopic differences
will necessarily make radiation damage a growing
concern.
There have been relatively few studies of the soft
X-ray radiation chemistry and radiation damage of
polymers [11,12], particularly when compared to the
numerous studies of the chemical effects of high
energy electrons, hard X-rays, and gamma radiation
[810,13,14]. In general, the radiation chemistry and
damage of polymers can take several forms, such as
loss of crystallinity, loss of mass, or chemical
modication [7]. We are primarily concerned here
with chemical modications as manifested in NEX-
AFS spectral changes, as NEXAFS spectroscopy is
the basis of compositional analysis in soft X-ray
microscopy.
The radiation chemistry of polymers and mole-
cules can vary strongly between resonant versus
non-resonant core excitation [1517]. As the chemi-
cal sensitivity of NEXAFS spectroscopy is strongest
at X-ray energies that correspond to specic resonant
Scheme 1. Chemical structures of polymers examined in this
* excitations (e.g. C 1sp transitions), the large
study.
literature of non-resonant electron, g and hard X-ray
irradiation may not be directly applicable to the
radiation damage that occurs in resonant or near (PE), and poly(propylene oxide) (PPO). The chemi-
resonant excitations. Experimental conditions and the cal structures of these polymers are presented in
impact of different characterization methods will Scheme 1.
vary between different studies, and may therefore not Chemical changes in the radiation-damaged poly-
be applicable to the specic environment in an X-ray mers were examined by comparing NEXAFS spectra
microscope. While our goal is to be as general as of the polymers acquired before and after soft X-ray
possible, we have studied the radiation damage of irradiation. Several different effects are observed: the
these polymers in situ in the experimental conditions loss of mass from the polymer lm; a decrease in
in which NEXAFS microscopy is performed (e.g. intensity of specic spectral features, attributed to
thin sections, He-rich environment, etc.). the loss of specic functional groups; and the
We have examined a series of polymers that span observation of new spectral features, attributed to the
a wide range of common polymer structures, with a formation of new chemical structures. The kinetics
primary focus on polymers that contain the carbonyl of mass loss and the formation or loss of specic
functional group: poly(methyl methacrylate) functional groups was measured for a series of
(PMMA), poly(bisphenol-A-carbonate) (PC), Nylon polymers using a damage-monitor image se-
6, poly(vinyl methyl ketone) (PVMK), poly(ethylene quence technique. The radiation induced mass
terephthalate) (PET), polyurethane (PU), poly- loss for all polymers is determined by measuring
(ethylene succinate) (PES). The easily damaged the rate of ablation as a function of X-ray exposure.
carbonyl group [8] has a narrow and readily identi- We develop a simple correlation that relates the
* able C 1s(C=O)p transition that allows the rate of loss of the carbonyl functional group to the
C=O
identication of numerous chemical moieties posses- carbonyl C 1s ionization potential, which is a simple
sing carbonyl functionality [18]. For comparison, we metric for the local chemical and electronic environ-
have also included polystyrene (PS), polyethylene ment of the carbonyl carbon atom. Finally, we
T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578 67
measure the difference in the radiation chemistry of cannot be easily measured, but the He ow rate was
polymers in the presence and absence of oxygen. kept constant for all quantitative damage experiments
The derived quantitative critical doses and quali- to best ensure a consistent atmosphere.
tative insights should be useful to X-ray microscopy For energy scale calibration, CO gas was added
2
practitioners in order to dene boundary constraints to the He purge in the microscope and the transmis-
for analytical experiments. sion spectrum of the mixture of the polymer and CO
2
gas was recorded [22,23]. The energies of the
CO Rydberg transitions from the high-resolution
2
NEXAFS spectra of Ma et al. [24] were used to
2. Experimental calibrate these spectra.
2.1. Sample origin and preparation
2.3. Detector and detector calibration
Thin lms (|50 to 200 nm) of the polymers were
prepared for this study. Samples of PVMK and PES The X-ray transmission of the sample was mea-
were obtained from Scientic Polymer Products, sured using a gas proportional counter mounted a
PMMA from Aldrich Chemical, and PS from Poly- few millimeters behind the sample. Several copies of
mer Laboratories. The polyurethane (PU, see the same detector design were used in the course of
Scheme 1) and poly(propylene oxide) (PPO) samples these experiments since the detector had a nite
were provided by Dow Chemical and have been operating lifetime. In order to properly account for
previously described [19]. The Nylon-6 sample was the exchange of detectors, two variables were con-
obtained from collaborators at AlliedSignal. The trolled: the detector position and the relative detector
molecular weight was not known or not dened for efciency. The variable sampledetector distance
all polymers. Differences in molecular weight should was measured and corrected for by accounting for
have a minimal inuence on the damage rate of the absorption of X-rays by the air / helium purge gas
specic functional groups but a larger effect on the mixture. It was not possible to measure the absolute
mass loss damage rates. efciency of the gas proportional counters against a
Thin polymer sections (|100 nm thick) of most known standard, although comparisons between the
polymers were prepared by ultramicrotomy, using a detected and anticipated photon count rates suggest a
LKB Nova microtome or a Reichert-Jung Ultracut S detector efciency between 10 and 40%. To account
cryo-ultramicrotome and were mounted on standard for the potential differences in efciency of different
TEM grids. Thin lms of PES and PS were prepared detectors, the rate of radiation damage for the C
* by solvent casting, from chloroform and toluene 1s(C=O)p transition in polycarbonate (PC)
C=O
respectively, and oated onto TEM grids. was used as an internal standard. The repeatability of
this damage rate in identical conditions (same detec-
tor, same atmosphere, and same sample thickness)
2.2. Microscope description was within 10%. This internal calibration method
provides a relative comparison suitable for the
Data for this study were acquired using the Stony internally consistent comparison of the radiation
Brook Scanning Transmission X-ray Microscope damage kinetics of different polymers. We have
(STXM) at the National Synchrotron Light Source assumed a detector efciency of 30% for our esti-
(NSLS) in Brookhaven, NY [20,21] during several mate of the absolute critical dose and G-values,
data acquisition runs. The STXM is operated at room cognizant that the systematic errors in these values
temperature and inside a He purge enclosure at might be as large or even larger than 100%. Never-
atmospheric pressure. The radiation damage studies theless, these results provide a meaningful com-
were performed in this helium-rich environment parison of the effect of soft X-ray exposure between
except for specic studies performed in air. The different polymers during NEXAFS microscopy
precise composition of the He purge atmosphere experiments.
68 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
2.4. Measurement of radiation damage where I and I are the transmitted and incident X-ray
0
ux, respectively, m is the energy dependent mass
A simple determination of the character of the soft absorption coefcient, r is the polymer density, and
X-ray radiation chemistry of the polymers examined t is the sample thickness.
in this study was obtained by comparing the NEX- The polymer lm region chosen for the damage-
AFS spectra of the virgin (undamaged) and the X-ray imaging series included an open area or a hole. The
irradiated polymer lms. These spectra were ac- X-ray transmission measured in this open area (i.e.
quired with a defocused beam so that the radiation the intensity in the image pixels corresponding to the
dose from the acquisition of these spectra would be hole) provided an internal and nearly instantaneous
below the threshold for observing radiation damage, measurement of the incident beam intensity (I ) at
0
based on the measured critical doses described the time the image was recorded. This internal I was
0
below. used to obtain the optical density of the material at
In this work, radiation damage was induced using the imaging energy (Eq. (1)). In the images used to
an X-ray energy in the C 1s ionization continuum monitor the radiation damage, these images provide
(315 eV). This energy is above the chemically the optical density of the particular feature used to
specic NEXAFS absorption features and where the monitor chemical change in the polymer, such as the
* X-rays are absorbed non-preferentially by all of the C 1sp transition. Since the featureless ioniza-
C=O
carbon atoms in the polymer. Quantitative determi- tion cross-section at 315 eV is proportional to both
nation of the polymer radiation damage kinetics was the sample thickness and density, the images used to
obtained through a series of X-ray imaging measure- damage the polymer at this energy also contain
ments performed in the X-ray microscope. A series the mass-thickness and can be used to measure
of images was acquired in which the material was the degree of mass loss from the polymer.
alternatively exposed to damaging photons by With increasing radiation dose (d), the optical
imaging at 315 eV, and then monitored at an energy density of a monitored spectral feature or the mass-
corresponding to a specic spectroscopic transition. thickness at 315 eV will change in a monotonic and
The effect of the radiation damage was measured by typically exponential way. In order to quantify the
imaging at the energy of a specic spectroscopic damage rate, the optical density has been tted to the
* feature, such as, for example, the C 1s(C=O)p following exponential expression:
C=O
excitation at 290.5 eV in polycarbonate (PC). The
* OD5OD 1C exp(2d/d ) (2) dwell time used in recording these images was
` c
adjusted so that the radiation exposure in the
damaging images at 315 eV was signicantly where OD is the remaining optical density after
`
greater than the radiation exposure from the moni- innite radiation dose, (C1OD ) is the optical
`
toring images. This exposure-monitor sequence density prior to irradiation, d is the radiation dose,
was repeated for about 50 image pairs. and d is the critical radiation dose. At the critical
c
radiation dose, 1/e or 63% of the total attenuation of
a specic spectroscopic feature (or mass-thickness)
has occurred. This metric can be used to compare the
3. Calculations
relative radiation sensitivity of different polymers
and different functional groups, as a smaller critical
3.1. Quantitative determination of the radiation
dose implies a faster damage rate. For mass loss, the
damage kinetics
value of OD from the t of Eq. (2) can also be used
`
to characterize the nature of the radiation chemistry.
Since NEXAFS spectroscopy measured in trans-
If the extrapolated optical density after innite dose
mission obeys Beers law, the optical density (OD)
tends to zero (i.e. OD 0), then the polymer loses
`
at any energy can be obtained from transmission
mass during radiation damage, while if the extrapo-
X-ray images as
lated OD is close to 1, the polymer is resistant to
`
OD5 2ln(I /I ) 5mrt (1) mass loss. Crosslinking and chain scissioning are
0
T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578 69
hypothesized as likely radiation damage outcomes geometries were determined using the program
based on these observations. GAMESS [28] with a 6-21G* level basis set. For the
GSCF3 calculations, a Huzinaga [29] basis set is
3.2. Ionization potential calculations employed: (621/ 41) contracted Gaussian type func-
tions were used on the heavy atoms (C, N and O);
To aid the discussion of the radiation damage rates (41) on H; and a higher quality basis set (411121/
and chemistry for these polymers, ab initio Improved 3111/ *) on the heavy atom onto which the core hole
Virtual Orbital (IVO) calculations have been per- is placed.
formed to determine the carbon 1s ionization po-
tential (IP) of the carbonyl carbon atom in a series of
polymers. The target polymers and the molecular 4. Results and discussion
models used for these calculations are presented in
Scheme 2. 4.1. Qualitative chemical and spectroscopic
Calculations on these species were carried out observations
using Kosugis GSCF3 package [25,26]. These
calculations are based on the Improved Virtual The nature of the chemical changes induced by
Orbital approximation (IVO) which explicitly takes radiation damage and the susceptibility towards mass
into account the core hole in the HartreeFock loss for many of the polymers investigated in this
approximation and are highly optimized for calcula- paper can be observed qualitatively in Figs. 1 and 2.
tions of core excited states [27]. The difference in Fig. 1 presents the NEXAFS spectra of polymers that
the total energy between the core ionized and ground lose mass upon X-ray irradiation (PET, Nylon-6,
states energies (DSCF) gives the core ionization PVMK, PMMA and PE) and Fig. 2 presents the
potential (IP) with a typical accuracy of 1 eV, NEXAFS spectra of some polymers that are totally
reecting the limitations of the IVO approximation. resistant to mass loss (PS, PC and PU) and by
Optimized (minimum total energy) molecular implication should crosslink under X-ray irradiation.
All spectra except that of PE have been acquired in a
He-rich environment.
Several general trends can be observed. In poly-
mers that contain carbonyl functional groups, a
* decrease in the intensity of the C 1s(C=O)p
C=O
transition is clearly observed. In the NEXAFS spec-
trum of irradiated PET (Fig. 1), a decay in the C
* 1s(CH)p transitions (284.8 and 285.4 eV) is
C=C
also observed in addition to the attenuation of the C
* 1s(C=O)p transition (289 eV) (previously
C=O
observed by Rightor et al. [11]). Similarly, PVMK
and Nylon-6 have a pronounced decrease in the C
* 1s(C=O)p transition (286.8 and 287.3 eV,
C=O
respectively), as well as the growth of a new feature
at |285 eV. The change in the intensity of the
* carbonyl C 1s(C=O)p absorption will be
C=O
used below to track radiation damage to the carbonyl
functional group as a function of radiation dose.
The observation of new spectroscopic transitions
at |285 eV in the NEXAFS spectra of many
irradiated polymers, including PE, PVMK, and
Scheme 2. Chemical structures of the molecular models used for
Nylon 6, are characteristic of unsaturated CC
ab initio Improved Virtual Orbital (IVO) calculations of the C 1s
ionization potential of the carbonyl group in a series of polymers. bonds (i.e. phenyl, ethylene and ethyne functional
70 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
Fig. 1. Comparison of the C 1s NEXAFS spectra of polymers that
predominantly lose mass upon irradiation: poly(ethylene tere-
phthalate) PET, Nylon-6 N6, poly(vinyl methyl ether)
PVMK, poly(methyl methacrylate) PMMA and polyethylene
Fig. 2. Comparison of the C 1s NEXAFS spectra of polymers that
PE, before () and after ( ? ) X-ray exposure. The
are resistant to mass loss: polystyrene PS, polycarbonate PC
total dose administered is indicated. PE was exposed in a He/ air
and polyurethane PU, before () and after ( ? )
mixture. The total dose has not been determined. The spectra are
X-ray exposure. The total dose administered is indicated.
included as an illustration of spectral changes due to damage. For
details about the dependence of PE damage on the presence of
oxygen, see text.
in the 286287 eV energy range in the spectra of the
* irradiated polymers. Typically, a C 1s(CR)p
C=C
groups). Additional new features can be observed in transition originating from the substituted phenyl
the NEXAFS spectrum of irradiated Nylon-6 (Fig. ring carbon atoms is present in this energy range
1), particularly a relatively well-resolved spectro- (e.g. CR atoms, where R are substituents with
scopic feature is introduced at 286.75 eV. The energy electron inductive properties). For example, in the
of this new feature closely corresponds to the C spectrum of virgin polyurethane (Fig. 2), the C
* * 1sp transition in a polyacrylonitrile [1,30] and 1s(CR)p transition at 286.5 eV is attributed
CN C=C
* acetonitrile [31], and the C 1sp transition in to phenyl ring carbon atom sites that are substituted
C=N
imidazole [32], which suggests that this new feature by the carbamate group [19], above the C 1s(C
* could be from the formation of C=N unsaturation in H)p transition from the CH phenyl carbon
C=C
Nylon-6. atoms. In all spectra of the radiation damaged
In polymers containing phenyl functional groups aromatic polymers, the energy range 286287 eV is
(PET, PS, PC, PU), new features are also observed lled in by broad or discrete transitions, sug-
T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578 71
gesting a modication of the phenyl rings is a
potential outcome of the radiation damage of these
polymers.
The chemical origin of these features and the
chemical pathways leading to them has not been
unambiguously identied, although NEXAFS spectra
provide valuable indications of the likely chemistry.
4.2. Mass loss observations
Fig. 3 presents the mass loss for a series of
polymers as a function of radiation dose. A summary
of the critical dose values and fractional mass
remaining at innite dose obtained from the t of the
data to Eq. (2) is presented in Table 1. Some
polymers undergo damage until no polymer would
remain for innite dose (OD 50), while others
`
would reach a nite, constant mass thickness
(OD .0). The polymers PU, PC, PS, and PE
`
exhibited negligible mass loss and the respective data Fig. 3. Summary of polymer mass loss results. The y-axis
represents the fraction of the polymer thickness remaining after
are not displayed in Fig. 3.
the indicated dose.
Polymers can lose mass due to bond breaking
Table 1
Summary of the rate and extent of chemical damage by mass loss for a series of polymers exposed in a He-rich environment. The critical
dose for mass loss represents the X-ray dose needed to reduce the projected sample thickness by 1/e, and the fractional mass is the mass
remaining after an extrapolation to innite exposure
a
Polymer Density Mass loss Fractional Propensity for crosslinking
3 b,c,d
(g/ cm ) critical dose mass,
Previous This
3
(eV/ nm ) OD /(OD 1C)
` `
work work
PC 1.2 None 1.0 Unknown Yes (strongly)
PU 1.24 None 1.0 Unknown Yes (strongly)
PES 1.175 830 0.32 Unknown Some
PMMA 1.2 350 0.72 Some [12] Yes
Nylon-6 1.12 800 0.85 Yes [8] Yes
PVMK 1.12 1400 0.74 Unknown Yes
PET 1.385 58,700 0 Some [33] No
PS 1.05 None 1.0 Yes [8] Yes (strongly)
PE 0.92 None 1.0 Yes [34] Yes (strongly)
PPO 1.0 430 0 No [8] No
a
Densities from Scientic Polymer Products compilation, http: / / www.scienticpolymer.com/ resources/ poly dens alpha.htm.
] ]
b
All experimental (relative) errors are estimated to be 10%. Systematic errors are dominated by uncertainty about the absolute detector
3 3
efciency and might be as large as 100%. The measured radiation dose is presented in eV/ nm rather than SI units of Grays, as eV/ nm can
be directly related to the measurement units of the microscope (spatial scale, sample thickness and photon energy).
c 3 5
Conversion: eV/ nm 5(1.602310 Grays) /r (where r is the polymer density).
d
Assumed 30% detector efciency.
72 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
(scissioning) in the main chain or in side groups. polymers tested, those with aromatic groups (PET,
While some polymers might undergo both scission- PS, PC, PU) lost less than 10% of their original mass
3
ing and crosslinking upon irradiation, one mecha- at a dose of 1500 eV/ nm . The ve polymers (PPO,
nism usually dominates. Scissioning is the dominant Nylon-6, PVMK, PMMA, and PES) that lost a
process in electron damage studies of PET [33] and signicant fraction (.10%) of their mass for this
PMMA [8,12,13]; crosslinking dominates in PE [34], dose do not contain aromatic groups. This result
while crosslinking and scissioning are considered to agrees with previous electron irradiation studies [8,9]
be comparable in Nylon-6 [8]. Based on the OD which indicate that the presence of aromatic groups
`
values shown in Table 1, our data is consistent with protect polymers from radiation damage. It is inter-
these previous results: PE and PS do not lose mass esting to note that aromatic groups seem to only
which can be attributed to high crosslinking, PET stabilize the polymers, but not to control the prefer-
loses mass, while Nylon has OD 50.85 and PMMA ence for scission or crosslinking (i.e. they change the
`
has OD 50.72, which would indicate that some rate but not the outcome). For example, our data
`
scissioning occurs, but that crosslinking is somewhat indicate that PET eventually completely scissions,
more dominant. Among the other polymers investi- but does so only very slowly, while PC, PS and PU
gated, PVMK both scissions and crosslinks, with a lost virtually no mass. An unexplored aspect is the
* slight dominance of crosslinking, PES predominantly effect that resonant C 1sp excitation and the
C=C
scissions, while PPO scissions completely. PU ex- potential for substantially different de-excitation
hibits negligible mass loss and therefore should be pathways will have on the radiation chemistry of
highly crosslinking. aromatic polymers.
Previous studies [8] suggest that a reasonable In addition to kinetic stabilization due to the
prediction of the propensity for crosslinking in presence of aromatic groups, crosslinking upon
polymers can be based on the structure of the irradiation can directly protect a polymer from mass
polymer backbone. Scheme 3 presents two general- loss. According to previous experiments [8], Nylon-
ized polymer structures: Structure A with the tertiary 6, PMMA, polyethylene, and polystyrene crosslink
backbone carbon atom highlighted, and Structure B, upon irradiation with electrons. Of these four poly-
with the quaternary backbone carbon atom high- mers, Nylon-6 retained 85% of its total mass and
lighted. Polymer chains with tertiary carbon atoms PMMA retained 72% of its total mass upon irradia-
are likely to crosslink, while polymer chains with tion with 315 eV X-rays, while polyethylene and
quaternary backbone carbons are likely to scission. polystyrene lost a negligible fraction of their mass.
We note that our data for the radiation damage of PS The spectra of Nylon-6 and polyethylene which were
and PVMK supports this prediction. However, most acquired after irradiation with soft X-rays show the
of the other polymers investigated cannot be tted growth of a new, broad peak at |285 eV(see Fig. 1),
* within this scheme on account of their more compli- where C 1sp transitions associated with C=C
C=C
cated chemical structure. unsaturation have been observed in many other
The presence of an aromatic group has a signi- species [35]. An increase in C=C bonds has been
cant impact on the damage rate of polymers. Of the associated with crosslinking in polymers such as PE
[8], but might arise in general from mechanisms that
are not directly related to crosslinking. In soft X-ray
irradiated PMMA, main chain and side chain scis-
sioning is the dominant damage mechanism. How-
ever, after sufciently large doses, PMMA might
crosslink [36]. This is due to the loss of the methyl
ester side chain, which has a 1:1 correspondence
with the formation of C=C bonds [13]. In damaged
PMMA, Zhang et al. attributed a feature at 286.6 eV
to C=C bonds and interpreted it as a sign of
Scheme 3. crosslinking [12,13], even though C=C bonds typi-
T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578 73
cally have a resonance near 285 eV. Our results show
slightly different spectral features for damaged
PMMA, but agree with prior results in as far as
PMMA retained a large percentage of its mass and is
thus crosslinking.
In PE, the formation of C=C bonds and the
appearance of a 285 eV feature is attributed to
hydrogen abstraction, which also leads to cross-
linking [8]. The 285 eV peak associated with cross-
linking is also present in the radiation-damaged
spectrum of poly(vinyl methyl ketone) (see Fig. 1).
Since PVMK retains a high percentage (74%) of its
mass after irradiation, it is likely that PVMK pre-
dominantly crosslinks upon irradiation.
4.3. Loss of carbonyl functional group
Polymers containing carbonyl groups have a
Fig. 4. Summary of carbonyl group loss results. The y-axis * characteristic C 1s(C=O)p transition that is
C=O
represents the normalized change in optical density at the carbonyl
useful for chemical analysis. This functional group is
transition.
known to damage easily, which will have a large
effect on the sensitivity of spectral analysis of these
materials. We have therefore determined a critical and PVMK), the critical dose calculated should be
dose for the loss of the carbonyl functional group close to the true critical dose. The uncertainty is
for the following polymers: PMMA, PC, Nylon-6, largest for PES, for which mass loss is a substantial
PVMK, PET, PU, and PES. The experimental data process and therefore the calculated critical doses
and a t of the dose dependence of the C should be used with some caution.
* 1s(C=O)p transition to Eq. (2) are displayed Table 2 summarizes the critical dose for the
C=O
in Fig. 4 for all polymers except for PET. carbonyl group, the atomic fraction of carbonyl
Since mass loss and chemical changes to a specic carbon atoms in the polymer, the carbonyl-normal-
functional group can occur simultaneously, the criti- ized damage rate, the G-value for this damage, and
cal dose obtained by tting the raw OD of the C the calculated C 1s ionization potential of the
* 1s(C=O)p transition to Eq. (2) will involve carbonyl carbon atom. The carbonyl-normalized
C=O
some uncertainty, particularly when the mass loss is radiation damage rate accounts for differences in the
unrelated to the damage of the carbonyl functional polymer stoichiometry, permitting a direct compari-
group. Since we do not have a priori knowledge of son of the carbonyl critical doses. The G-values in
the detailed mechanisms for mass loss, we can only Table 2 are inversely related to the un-normalized
evaluate the critical dose of the optical density for critical doses in that they quantify the extent of
* the C 1s(C=O)p transition intensity. This radiation damage for a given dose [8]. The carbonyl
C=O
parameter substitution can either under- or overesti- G-values calculated provide a measure for carbonyl
mate the actual critical dose for the carbonyl group events per 100 eV dose to the whole sample. For
itself, since this intensity is convoluted with the loss polymers that exhibit signicant mass loss, the G-
of the polymer itself. For polymers that lose no mass, values calculated have relatively large uncertainty,
such as PU and PC, there will be no additional but are included in order to facilitate comparison
uncertainty. For polymers where the mass loss is with previous electron irradiation studies. A direct
small relative to the attenuation of the C comparison might be limited by the experimental
* 1s(C=O)p transition (i.e. Nylon-6, PMMA differences in sample environment and the particular
C=O
74 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
Table 2
Summary of the chemical damage rates of the loss of the carbonyl functional group for a series of polymers exposed in a He-rich
environment, in comparison to the calculated C 1s ionization potential for the carbonyl carbon atom in these polymers
Polymer C=O [ C=O carbon Normalized G-value Calculated
damage atoms to total [ C=O C 1s C=O
a,b a
rate carbon atoms damage rate ionization
3 3
(eV/ nm ) per monomer (eV/ nm ) potential (eV)
PMMA 520 1/ 5 104 0.86 295.43
PES 530 2/ 6 177 1.10 295.98
PC 580 1/ 16 36 0.31 297.79
PU 740 2/ 13 114 0.43 296.63
PVMK 1600 1/ 4 400 0.38 294.00
Nylon6 2300 1/ 6 383 0.17 294.58
PET 22,000 2/ 10 4400 0.03 295.87
a
All experimental (relative) errors estimated 65%. Systematic errors are dominated by uncertainty about the absolute detector efciency
3 3
and might be as large as 100%. The measured radiation dose is presented in eV/ nm rather than SI units of Grays, as eV/ nm can be directly
related to the measurement units of the microscope (spatial scale, sample thickness and photon energy).
b
Assumed 30% detector efciency.
criterion used to judge an event (here, 63% of number of heteroatoms around the core-excited
maximum NEXAFS spectral change). atom. We note that previous studies have shown that
Using the carbonyl-normalized critical dose val- uorocarbons which have a higher relative ioniza-
ues, we see that the carbonyl group in polycarbonate tion potential [37] are very radiation sensitive
has a higher propensity towards damage than all [38], and that carbamate functional groups (NH
other polymers, including the aliphatic poly(ethylene C(O)OR) damage more readily than urea (NH
succinate). We note a somewhat surprising but C(O)NH) functional groups present in polyurethane
potentially useful correlation between the carbonyl- foams [3]. Further, the substantially more rapid mass
normalized critical dose and the calculated ionization loss observed for poly(propylene oxide) (PPO) than
potential of the carbonyl C 1s atom, which can be in PE supports a model in which more damage
observed from Fig. 5. In general, carbonyl carbon occurs faster for polymers with polarized bonds or
atoms with a higher C 1s ionization potential have a more oxygen atoms. The overall correlation in the
lower critical dose. The ionization potential is depen- present study and these other supporting observations
dent on the local electron density of the carbon atom suggest a relationship between the sensitivity of
site, which varies with the electronegativity and carbonyl functional groups to radiation damage and
their local chemical environment. We observe about
an order of magnitude more damage to a carbonate
functionality than to a ketone. The one exception to
this correlation to note is PET. In PET, the carbonyl
* groups are stabilized by p delocalization [11], i.e.
mixing of carbonyl and aromatic p orbitals, which is
more extensive than in the other polymers. This may
add aromatic stabilization to the carbonyl functional
groups.
Also of note is the substantially lower 7700 eV/
3
nm critical dose reported by Rightor et al. [11]. A
possible explanation might be that Rightor et al.
exposed the polymer with a focused beam in a single
spot, while we raster-scanned the beam to expose a
Fig. 5. Normalized carbonyl critical dose vs. ionization potential
of the carbonyl carbon. larger area. This would suggest a potential dose rate
T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578 75
dependence in the radiation damage kinetics, a theme
not explored in this paper. In addition, the spectral
shapes observed by Rightor after damage are slightly
different than in the data of this study. Specically,
the spectral feature of the carbonyl group at 288.2 eV
is higher relative to other features in our data, while
the feature at 289.1 eV appears equally damaged in
both data sets. We will show explicitly (Section 4.4)
that the relative oxygen content in the sample
environment plays a crucial role in the evolution of
* the C 1s(C=O)p transition intensity (288.2 eV
C=O
in PET), and differences in sample environment
between the Rightor et al. and our data might
account for the observed differences. Since all
samples for the data presented here have been
exposed in the same manner and with identical
helium ow rates during two data runs, a comparison
between different polymers within our data sequence
is self-consistent and meaningful.
Fig. 6. A comparison of fractional mass loss upon irradiation for
4.4. Effect of atmospheric oxygen on the radiation polyethylene damaged in air (an oxygen-rich environment) and in
a helium-rich environment. The PE irradiated in air only received
damage chemistry
a low total dose due to the rapidity of its mass loss.
The atmosphere in which the polymer is exposed
to radiation can drastically affect the nature and rate
of the radiation damage. In an inert atmosphere, such
as vacuum or an unreactive gas, X-ray generated
radicals are understood to be more stable [8]. In an
atmosphere containing oxygen, the radicals can react
to form peroxides or hydroperoxides [8,14], or
oxygen itself can be photoexcited or photoionized
and become reactive, accelerating the rate of radia-
tion degradation or the extent of the radiation
damage [8,14].
To explore the effect of the atmosphere on the
radiation chemistry of polymers, PE and PET were
irradiated in air in addition to the helium-rich
environment presented above. These results are
presented in Fig. 6 and 7, respectively. We note
immediately that both PE and PET lose mass at a
much faster rate when oxygen is present. The critical
dose for mass loss from PET is nearly two orders of
magnitude smaller in an oxygen-containing environ-
3
ment (600 eV/ nm ) than in a helium-ushed en-
3
Fig. 7. Comparison of fractional mass loss upon irradiation for
vironment (58,700 eV/ nm ). In both cases, the
polyethylene terephthalate damage in air (an oxygen-rich environ-
extrapolated thickness at innite dose is zero, that is,
ment) and in a helium-rich environment (the data for the PET
PET completely scissions. For PE, the results are
damaged in a helium-rich environment have a large scatter due to
even more remarkable. For PE damaged in air, the noise in the incident X-ray beam).
76 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
3
critical dose for mass loss was 400 eV/ nm , and the linking for irradiation in a vacuum. Therefore, the
extrapolated thickness at innite X-ray dose is zero. presence of oxygen dramatically changes the chemi-
In contrast, PE loses a negligible fraction of its mass cal pathways under which radiation damage to the
in a helium-rich environment. polymer occurs.
The presence of oxygen also has a dramatic effect The radiation damage and chemistry of PET is
on the radiation chemistry of PE. Fig. 8 presents the also quite different in the presence of oxygen. The
* change in the intensity of the 285 eV C 1sp peak at 288.3 eV in the C 1s NEXAFS spectrum of
C=C
transition as a function of dose, for PE irradiated in PET (Fig. 1) has been assigned as the C
* air and in a He-ushed environment. This C 1s(C=O)p transition of the carbonyl group
C=O
* 1sp transition is a classic sign of radiation [11,39]. In a helium-ushed environment, this car-
C=C
damage in saturated polymers, and has been associ- bonyl transition decays with a critical dose of 22,000
3
ated with polymer crosslinking through carboncar- eV/ nm (see Fig. 9). In air, the optical density at
bon double bond formation from photo-radicals on 288.3 eV decreases much more rapidly upon irradia-
adjacent polymer chains. For irradiation in air, an tion, with a critical dose for this decrease of 1900
3
* increase in the C 1sp transition is not ob- eV/ nm . Much of this decrease in critical dose can
C=C
served. In a helium-rich environment, an increase of be attributed to increased mass loss in the presence
the X-ray absorption of this transition is observed, of oxygen. However, when normalizing for the mass
3
with a critical dose of 260 eV/ nm (1/e dose for the loss, the OD at 288.3 eV is actually increasing
increase in the intensity of this feature, see Ref. slightly. NEXAFS spectra of PET irradiated in air
[11]). Similar behavior has been observed for elec- were not obtained.
tron and g-irradiation damage in polypropylene: These observations, and the discrepancy to Right-
degradation in the presence of oxygen, but cross- or et al. [11] for the critical dose for PET, indicate
Fig. 8. Changes in the optical density at 285 eV upon irradiation Fig. 9. Fractional change in optical density at 288.3 eV (energy
* for polyethylene damaged in air (an oxygen-rich environment) and corresponding to the C 1sp transition) upon irradiation for
C=O
in a helium-rich environment. The optical density at 285 eV is polyethylene terephthalate damaged in air (an oxygen-rich en-
scaled by normalizing the optical density at 315 eV to 1. vironment) and in a helium-rich environment.
T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578 77
that the polymer damage and radiation chemistry are effects of different environments upon radiation
sensitive to the acquisition conditions in the X-ray chemistry: we determined that irradiating polymer
microscope. samples in an oxygen-rich environment causes more
extensive and faster mass loss than in an inert
environment. The radiation chemistry of polymers
5. Conclusions damaged in an oxygen-rich vs. an inert environment
is also drastically different.
This paper presents a detailed description of soft Future, rened experiments regarding radiation
X-ray radiation damage to several polymers under damage of polymers in a STXM could include the
typical operating conditions in a STXM. We accom- control over some or all of the following variables:
plished this by: dose rate, sample thickness, molecular weight, use of
radical scavengers and antioxidants, and the oxygen
(i) Acquiring NEXAFS spectra of virgin and level in the He environment. Improvements in instru-
radiation damaged polymers to look at the spe- mentation presently under way to better control the
cic chemical changes caused by soft X-ray He environment should prove to be helpful in
irradiation. minimizing radiation damage.
(ii) Characterizing the rate and the extent of mass
loss in polymers irradiated by soft X-rays.
(iii) Characterizing the rate and the extent of
Acknowledgements
chemical change by tracking the loss of a specic
chemical group.
We would like to thank R. Spontak, V. Knowlton,
(iv) Examining the effect of atmosphere on the
and A.P. Smith for their assistance in polymer
radiation damage by soft X-rays.
ultramicrotomy. These data were acquired using the
Stony Brook STXM developed by the groups of C.
By documenting NEXAFS spectral changes, we
Jacobsen and J. Kirz from SUNY at Stony Brook
hope to provide an initial catalog of damaged
with support from the Ofce of Biological and
spectra for users of NEXAFS and EELS spectros-
Environmental Research, U.S. DOE under contract
copy tools. By examining the rate and extent of mass
DE-FG02-89ER60858, and the NSF under grant
loss, we explored some general rules for polymer
DBI-9605045. We thank C. Jacobsen for making his
mass loss: polymers that contain aromatic groups
stack code [40] available to us for adaptation for
and/ or crosslink upon irradiation are more resistant
this experiment, and Sue Wirick for microscope
to mass loss than polymers which do not contain
maintenance and support. Zone plates utilized were
aromatic groups or scission upon irradiation. By
developed by S. Spector and C. Jacobsen of Stony
examining the rates of chemical changes, we de-
Brook and Don Tennant of Lucent Technologies Bell
veloped a rule of thumb for chemical group loss: the
Labs, with support from the NSF under grant ECS-
susceptibility of a chemical group to radiation dam-
9510499. We most gratefully acknowledge technical
age depends on the local electronic structure
assistance by A. Scholl and D.A. Winesett in the
quantied here by the ionization potential of the
acquisition of the damage spectrum of PE. A
chemical group. We noted that as the ionization
GAANN fellowship and an NSF Young Investigator
potential of the chemical group investigated here
Award (DMR-9458060) supported this work.
increases, the susceptibility of that group to radiation
damage also increases. We believe that these rules of
thumb will aid users of soft X-ray and even electron
analysis techniques by providing them a comparative
References
method for choosing the spectral and image acquisi-
tion times which will not cause extensive damage to
[1] H. Ade, X. Zhang, S. Cameron, C. Costello, J. Kirz, S.
their polymer samples. Finally, we analyzed the Williams, Science 258 (1992) 972.
78 T. Coffey et al. / Journal of Electron Spectroscopy and Related Phenomena 122 (2002) 6578
[2] S. Zhu, Y. Liu, M.H. Rafailovich, J. Sokolov, D. Gersappe, [21] M. Feser, M. Carlucci-Dayton, C. Jacobsen, J. Kirz, U.
D.A. Winesett, H. Ade, Nature 400 (1999) 49. Neuhausler, G. Smith, B. Yu, in: I. McNulty (Ed.), X-ray
[3] S.G. Urquhart, A.P. Hitchcock, A.P. Smith, H.W. Ade, W. Microfocusing: Applications and Techniques, SPIE. Proc,
Lidy, E.G. Rightor, G.E. Mitchell, J. Electron Spectrosc. Vol. 3449, 1998, pp. 19.
Relat. Phenom. 100 (1999) 119. [22] A.P. Smith, T. Coffey, H. Ade, in: J. Thieme, G. Schmahl, E.
[4] H. Ade, S. Urquhart, in: T.K. Sham (Ed.), Chemical Applica- Umbach, D. Rudolph (Eds.), X-ray Microscopy and Spec-
tions of Synchrotron Radiation, World Scientic, Singapore, tromicroscopy, Springer, Berlin, 1997.
2001. [23] H. Ade, A.P. Smith, H. Zhang, G.R. Zhuang, J. Kirz, E.
[5] R.F. Egerton, Electron Energy Loss Spectroscopy in the Rightor, A. Hitchcock, J. Electron Spectrosc. Relat. Phenom.
Electron Microscope, Plenum Press, New York, 1986. 84 (1997) 53.
[6] M.M. Disko, C.C. Ahn, B. Fultz (Eds.), Transmission [24] Y. Ma, C.T. Chen, G. Meigs, K. Randall, F. Sette, Phys. Rev.
Electron Energy Loss Spectrometry in Materials Science, A 44 (1991) 1848.
Minerals, Metals and Materials Society, Warrendale, 1992. [25] N. Kosugi, Theor. Chim. Acta 72 (1987) 149.
[7] D. Vesely, D. Finch, Electron Microsc. Anal. 7 (1985). [26] N. Kosugi, H. Kuroda, Chem. Phys. Lett. 74 (1980) 490.
[8] K. Dawes, L.C. Glover, Effects of Electron Beam and [27] W.J. Hunt, W.A.I. Goddard, Chem. Phys. Lett. 3 (1969) 414.
g-Irradiation on Polymeric Materials, AIP Press, Woodbury, [28] M.W. Schmidt, K.K. Baldridge, J.A. Boatz et al., J. Comput.
NY, 1996. Chem. 14 (1993) 1347.
[9] L.C. Sawyer, D.T. Grubb, Polymer Microscopy, Chapman [29] S. Huzinaga, J. Andzelm, M. Klobukowski, E. Radzio-
and Hill, New York, 1987. Andzelm, Y. Sasaki, H. Tatewaki, Gaussian Basis Sets for
[10] G. Beamson, D. Briggs, High Resolution XPS of Organic Molecular Orbital Calculations, Elsevier, Amsterdam, 1984.
Polymers: The Scienta ESCA300 Database, Wiley, New [30] A.P. Hitchcock, I. Koprinarov, T. Tyliszczak et al., Ultramic-
York, 1992. roscopy 88 (2001) 33.
[11] E.G. Rightor, A.P. Hitchcock, H. Ade, R.D. Leapman, S.G. [31] A.P. Hitchcock, M. Tronc, A. Modelli, J. Phys. Chem. 93
Urquhart, A.P. Smith, G. Mitchell, D. Fisher, H.J. Shin, T. (1989) 3068.
Warwick, J. Phys. Chem. B 101 (1997) 1950. [32] E. Apen, A.P. Hitchcock, J.L. Gland, J. Phys. Chem. 97
[12] X. Zhang, C. Jacobsen, S. Lindaas, S. Williams, J. Vac. Sci. (1993) 6859.
Technol. B 13 (1995) 1477. [33] D.T. Turner, in: M. Dole (Ed.), The Radiation Chemistry of
[13] J.A. Moore, J.O. Choi, Degradation of Poly(Methyl Meth- Macromolecules, Vol. II, Academic Press, New York, 1973,
acrylate): Deep UV, X-ray, Electron-beam, and Proton-beam pp. 137.
Irradiation, American Chemical Society, 1991. [34] B.J. Lyons, Radiat. Phys. Chem. 22 (1983) 135.
[14] J.H. ODonnell, Chemistry of Radiation Degradation of [35] A.P. Hitchcock, D.C. Mancini, J. Electron Spectrosc. Relat.
Polymers, American Chemical Society, 1991. Phenom. 67 (1994) 1.
[15] M.C.K. Tinone, K. Tanaka, J. Maruyama, N. Ueno, J. Chem. [36] E.M. Lehockey, I. Reid, I. Hill, J. Vac. Sci. Technol. 6
Phys. 100 (1994) 5988. (1988) 2221.
[16] D.M. Hanson, Adv. Chem. Phys. 77 (1990) 1. [37] W.L. Jolly, K.D. Bomben, C.J. Eyermann, At. Data Nucl.
[17] E. Ikenaga, K. Isari, K. Kudara, Y. Yasui, S.A. Sardar, S. Data Tables 31 (1984) 433.
Wada, T. Sekitani, K. Tanaka, K. Mase, S. Tanaka, J. Chem. [38] B.J. Lyons, Radiat. Phys. Chem. 45 (1995) 159.
Phys. 114 (2001) 2751. [39] S.G. Urquhart, A.P. Hitchcock, A.P. Smith, H. Ade, E.G.
[18] S.G. Urquhart, H. Ade, J. Stohr (submitted for publication). Rightor, J. Phys. Chem. B 101 (1997) 2267.
[19] S.G. Urquhart, H.W. Ade, A.P. Smith, A.P. Hitchcock, E.G. [40] C. Jacobsen, S. Wirick, G. Flynn, C. Zimba, J. Microsc. 197
Rightor, W. Lidy, J. Phys. Chem. B 103 (1999) 4603. (2000) 173.
[20] X. Zhang, H. Ade, C. Jacobsen, J. Kirz, S. Lindaas, S.
Williams, S. Wirick, Nucl. Instrum. Meth. A A347 (1994)
431.