Contents I. Introduction
I. Introduction 519 UV laser ablation of polymers was discovered 20
II. Photochemical Ablation 522 years ago.1,2 This effect has many fascinating ap
A. Photochemical Modification 522 plications in lithography, micromechanics, and medi
B. SingleStep Model 524 cine. For the last 20 years, more than 103 papers
C. Surface Photochemical Etching (The 525 describing this phenomenon were published (see, e.g.,
FrenkelWilson Approach) comprehensive reviews, refs 37). Despite the high
D. Single Step Model. Results and Discussion 526 research activity, the nature of UV laser ablation of
E. Photochemical Theory of Laser Ablation. The 527 polymers is still far from being fully understood, e.g.,
Stefanlike Approach one can find contradictory interpretations of the same
F. Examples. The SingleStep Model 529 results in different papers.
G. Temperature Estimations 530 Originally, UV laser ablation of polymers was
III. Photothermal Ablation 531 believed to be a pure photochemical effect, resulting
from the direct bond breaking by UV photons.810
A. Surface Photothermal Model 531
Gradually, investigators obtained evidence that laser
B. Bulk Photothermal Model 535 heating of materials is significant and a pure thermal
C. Stefanlike Bulk Photothermal Model 536 nature of laser ablation was considered.1113 Here we
D. Stationary Wave Solution in Stefanlike Model 536 use the term “photothermal”7 for the process result
E. Transient Regimes 538 ing from laser heating of material.
F. Kinetics and Dynamics of Ablation. Depletion 540 Polymers are complex materials; therefore, laser
of Species and Real Ablation ablation of polymers is also a complicated phenom
IV. Subpicosecond Ablation 542 enon. In this paper, we will focus on the models of
A. Bulk and Surface Models 542 laser ablation. In addition, we inevitably have to
B. Kinetics of Single and TwoUSLP Ablation 542 answer the question of what are the specific features
C. Dynamics of USLP Ablation 544 of laser ablation of polymers that distinguish them
D. Photophysical Ablation 545 from the laser ablation of other materials (metals,
V. Photochemical + Photothermal Models 547 semiconductors, inorganic dielectrics, molecular sol
VI. The Role of Mechanical Stresses 548 ids).
VII. Conclusions 550 There are several approaches to modeling of poly
mer ablation. The authors of this paper represent one
VIII. Acknowledgment 550
of the “schools”; thus, our view of the problem is
IX. References 550 somewhat subjective.
Despite the complex nature of laser ablation, we
However, there is some difficulty in rightly prefer to develop simplified models (e.g., “pure”
determining the objects which we distinctly photochemical or “pure” photothermal), and analyze
conceive. them in detail to be able to assign specific features,
Rene Descarte which are experimentally observed for a particular
The name “laser ablation” is used generally to ablation mechanism.
describe the explosive lasermaterial interaction, We start with the photochemical model. In fact, the
a more appropriate definition that does not first consideration of laser ablation10 employed a very
imply a mechanism. simple but constructive idea that takes into account
Site of the Lawrence Berkeley National the specific feature of polymer materials. This idea
Laboratory is that polymers consist of long molecular chains with
Thus, the definition of thinking is the creation strong, covalent, bonds inside. At the same time,
and manipulation of symbols. molecules belonging to different chains interact
Richard F. Taflinger weakly. Therefore, polymer material becomes simple
molecular solid (i.e., easily removed material), if we
break the long polymer chains into small pieces by
* Corresponding author, email: bit@appl.scinnov.ru.
† Institute of Applied Physics Russian Academy of Sciences. direct photochemical effect (UV photons are consid
‡ Data Storage Institute. ered to have energy pω exceeding the energy of
10.1021/cr010426b CCC: $44.00 © 2003 American Chemical Society
Published on Web 01/28/2003
520 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
Nikita Bityurin was born in Nizhny Novgorod (Gorky), Russia, in 1954. Hong Minghui was born in Fujian, China, in 1965. He received his B.S.
He graduated from Nizniy Novgorod State University in 1977, and received and M.S. from Physics Department, Xiamen University, in 1985 and 1988.
his Ph.D. from Institute of Applied Physics Russian Academy of Sciences After teaching in Xiamen University as an Assistant Professor from 1988
(IAP RAS). He has been with IAP RAS since 1977. During 1993−2002, to 1994, he continued his M.E. (1996) and Ph.D. (2000) study in National
he worked also as an Invited Researcher at Johannes Kepler University, University of Singapore. He joined Laser Microprocessing Group, Data
Linz, Austria, LPL and LIMHP CNRS Laboratories, Villetaneuse, France, Storage Institute, Singapore, in 1995 as a research engineer. Currently,
Data Storage Institute, Singapore, and as an Invited Professor at University he is the principal research engineer and deputy manager of the group.
ParisNord, France. His scientific interest is laser−matter interaction His research interest includes laser ablation and related applications.
including laser effects on polymers, biological tissues and sol−gel materials.
He published more than 70 papers in referred journals. At the moment,
he is in the temporary position of the Head of Laboratory for Laser
Processing of Materials at IAP RAS.
Chong Tow Chong obtained his B.Eng. degree from the Tokyo Institute
of Technology, his M.Eng. degree from the National University of
Singapore, and his Sc.D. degree from the Massachusetts Institute of
Technology, all in Electrical Engineering. He is currently the Director of
Boris Luk’yanchuk was born in Volgograd, Russia, in 1944. He graduated the Data Storage Institute under the Agency for Science, Technology &
from the Moscow State University in 1967, and received his Ph.D. (1979) Research and hosted by the National University of Singapore. Dr Chong’s
from the P. N. Lebedev Physical Institute, Russian Academy of Sciences research interest is in the field of magnetic and optical data storage,
and Doctor of Sciences (1991) from the General Physics Institute, Russian especially in advance thin films for ultrahighdensity recording. He is also
Academy of Sciences, and Professor’s degree since 1992. During 1980− a Professor with the Department of Electrical and Computer Engineering,
2000 was working as senior researcher and Head of the Laboratory at NUS. His other research interests include highspeed electronic and optical
the General Physics Institute, Russian Academy of Sciences. Since 2000, devices. Dr. Chong has authored and coauthored more than 120
he is working as member of technical staff of Data Storage Institute, publications in international refereed journals, presented 20 invited talks,
Singapore. During 1989−2000, he was working as invited Professor in and holds 16 patents. He serves as cochairman of APMRC2002 and as
Johannes Kepler University, Linz, Austria, where he was awarded the member of the Technical Program Committee for ODS (USA), ISOM
title of Honorary Professor (1991). He was invited Professor at Faculté (Japan), MORIS (Japan), CLEO Pacific (USA), and OECC (Japan).
des Sciences de Luminy (Marseille, France), at Lecce University (Italy),
and Tokyo Institute of Technology (Japan). He has published five laser pulse, R is the absorption coefficient, Φ is the
monographs and more than 200 papers related to lasermatter interactions.
laser fluence, and Φth is the threshold fluence. This
covalent bond). Taking into account the Bouguer threshold fluence provides at the surface the frag
LambertBeer intensity distribution inside the ma ments of polymer chains smaller than some charac
terial, this simplified consideration yields the so teristic length.7 Typical value of this threshold flu
called “photochemical law”:7 ence for polyimide and UV radiation with λ ) 193
{
nm is about 15 mJ/cm2.
0, if Φ < Φth Many authors used the dependence he ) he(Φ) (we
he ) 1
R
log
Φ
Φth [ ]
if Φ g Φth
(1) will call it kinetic curve) given by eq 1 to describe
their experimental results. Later it was found that
the value of R obtained by fitting the kinetic curve
Here he is the etch depth (per pulse), which is to experimental data could significantly differ from
considered as a thickness of material, ablated per the measured absorption coefficient. It leads to the
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 521
Table 1. Calculated from Thermal Model and heating. Here heat diffusion is taken into account,
Experimental Values13 of the Threshold Fluence and, most importantly, the ablation is associated with
radiation λ, R, Φth, mJ/cm2, Φth, mJ/cm2, the chain breaking process, which obeys the Arrhe
nm 105 cm1 R theory experiment13 nius law.
351 0.32 0.1 102 105 The introduction of the moving interface was a
308 1 0.11 46 46 breakthrough from the point of view of modeling.
248 3.1 0.12 29 25 Now it has been proved experimentally24 that the
193 4.25 0.07 26 15
interface between gaseous products of ablation and
condensed material moves during the nanosecond
idea of modification of optical properties of material laser pulse.
during the pulse. This modification can be either Historically, the problem with the moving interface
nonreversible (leading to “incubation”) or tran was first considered in connection with the kinetics
sient.14,15 of the firstorder phase transitions (movement of the
In some papers, the kinetic curve is calculated melting front; see ref 7). Another problem with the
based on the following consideration. The etch depth moving interface was applied for the laser evapora
at a given fluence is considered as the distance from tion of metals.25 There were several early attempts
the surface at which the amount of absorbed energy to construct models with a moving interface relating
per unit of volume equals the threshold one. The the problem of laser ablation of polymers.2631 These
latter can be found from the data on ablation thresh models are photochemical (even the model developed
old. Usually it is implied that this absorbed energy in ref 29 where the position of the front is associated
provides a photochemical chain breaking; thus, these with the critical temperature, but the temperature
models can be treated in a similar way as photo is calculated by eq 2).
chemical.1519 Real thermal models with a moving interface
Photothermal modeling is another way to describe following the model of ref 25 were developed for laser
polymer ablation. It was understood that the ab ablation of polymers in refs 3236. We call them the
sorbed energy produces an elevated temperature high “surface photothermal models” because they assumed
enough for thermal destruction of the polymer. In ref photothermal destruction of the material within a
20, the etch depth is calculated as a penetration of very thin surface layer. It is similar to evaporation
isotherm where the temperature reaches its “critical” of heated material into vacuum. The velocity V of
value, T ) Tcr. Neglecting the heat diffusion one can ablation front follows the Arrheniuslike law:
write the adiabatic approximation for the increase
in temperature: V ) V0 exp[Ea/kBTs] (4)
dT RI
) (2) Here V0 is of the order of sound velocity in condensed
dt cpF
phase, Ea is the activation energy of evaporation, kB
Here I is the light intensity at a particular point, is the Boltzmann constant, and Ts is the surface
cp is the heat capacity, and F is the density. Using temperature.
the BouguerLambertBeer intensity distribution, The consideration of moving interface problems
one arrives at the “photochemical law” (eq 1) for the immediately yields that the kinetic curve (near and
etch depth, where the threshold intensity is given by above the threshold) should be linear rather than
logarithmic. The logarithmic law (eq 1) at relatively
cpFTcr high fluences is caused by attenuation of coming laser
Φth ) (3) radiation within the plume. Thus, R in eq 1 is rather
R(1  R) Rp, a plume absorption coefficient recalculated per
where R is the reflection coefficient. ablated depth, or Lagrange absorption coefficient of
From a mathematical point of view, there is no the plume. The absorbed laser intensity at the
difference between the aboveformulated photochemi ablated surface is given by
cal and photothermal models, i.e., the temperature
plays the role of a “photochemical” variable. The both Is(t) ) (1  R)I0(t) exp[ Rphe(t)] (5)
considerations yield the law (eq 1). Differences ap
pear if one takes into account the heat diffusion.20 A where I0 is incident laser intensity.
crude estimation can be done by replacing R1 f All the models considered in this paper are the
R1 + 2xDTtp in eq 3. Here DT is the heat diffusivity models with a moving interface. We consider two
of polymer, and tp is the duration of a laser pulse. types of such models, the socalled “Stefanlike” and
For illustration, we present in Table 1 the calculated “FrenkelWilsonlike” problems.
values of the threshold fluence for laser ablation of With Stefanlike problems, the position of a moving
polyimide by radiation of excimer lasers. The follow interface is related to some critical value of the main
ing values of parameters are used: F ) 1.4 g/cm3, variable. For example, in the classical Stefan problem
cp ) 2.2 J/g K, DT ) 103 cm2/s, Tcr ) 850 K, tp ) of the melting front propagation it is melting tem
15 ns. Experimental values of R, R, and Φth are also perature. In the theory of laser ablation of polymers,
presented in Table 1. One can see a very close it would be rather the critical fracture of broken
correspondence of calculated and experimental re bonds. The position of interface within the Stefan
sults. In refs 2123, the ablation is considered as a like problem is given in implicit form, similar to the
thermal destruction of polymer resulting from laser position of the melt front, i.e., T (z ) zmelt.front) ) Tmelt.
522 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
In the FrenkelWilsonlike formulation, the velocity increase in the volume of destruction products during
of a moving interface is a known function of values the depolymerization of poly (methyl methacrylate)
of variables at the surface. For example, for the (PMMA). Another reason is the creation of volatile
melting problem one can write at some approxima species, which produce inner pressure. There are
tion (see in ref 7) models of laser ablation that relate the effect of
ablation to some critical value of inner pressure.60
dzmelt.front In fact, these models come to the theory of polymer
Vmelt.front ) ∝ [T(z ) zmelt.front)  Tmelt] ablation from the theory of IR laser ablation of soft
dt
biological tissues. Here laser heating results in inner
evaporation of water providing highpressure inside
Thus, overheating is a necessary condition for mo the tissue. We consider in section VI how mechanical
tion of the melt front, i.e., melting occurs only with stresses can be incorporated in the models developed
T(z ) zmelt.front) > Tmelt. The classical surface photo in the previous sections.
thermal model (eq 2) is also of the FrenkelWilson In the present paper, we do not address hydrody
type because here the ablation velocity is a known namic and gasdynamic aspects of laser ablation.
function of surface temperature. Gasdynamics of ablation is discussed in the recent
The paper is organized as follows. In section II, we review paper ref 61 and in refs 6264.
consider the macrokinetic aspect of photochemical We also do not consider melting65 and topology of
modification of polymers from a mathematical point crater formation during ablation66 as well as a very
of view. The photochemical modification of polymers important question of stability of plain ablation
under UV laser irradiation is their inherent feature front67 and structure formation.6871 We believe that
(chain breaking is also a modification). Following refs these problems will be discussed in a future review
3740, we formulate both FrenkelWilson and Ste paper.
fanlike approaches to pure photochemical ablation.
The main problem with the pure photochemical
models is their selfconsistency in the sense that we II. Photochemical Ablation
have to calculate the temperature rise which ac
companies photochemical ablation. If the tempera A. Photochemical Modification
ture is high enough to provide thermodestruction of Let us consider a laser beam propagating along the
the material, then the pure photochemical model is z axis, the halfspace z > 0 being occupied by the
not reliable. This question is also discussed in section initially homogeneous dielectric media. We will evalu
II. ate equations that describe the photochemical modi
In section III, we consider pure photothermal fication of material in quite a general form. But first
models of laser ablation. We start with the well we consider the simplest photochemical reaction
understood surface photothermal model.35,36 Then we
consider the Stefanlike and FrenkelWilson formula pω
A 98 B (6)
tion of the socalled bulk or volume model where laser
ablation proceeds through the chain scission caused Here A stands for the element of the initial mate
by laser heating of material followed by surface rial, and B denotes the product of photochemical
evaporation of degradation products.4144 We compare reaction. The kinetics of modification caused by eq 6
the predictions of these models concerning ablation is described by the equations:
by nanosecond pulses.
In section IV, we consider application of these ∂NA ηAσA
models for ablation by subpicosecond pulses. We ) N I
compare predictions of surface and bulk models. Also ∂t pω A
we discuss here a model that is somewhat intermedi ∂I
ate between photothermal and photochemical ones. ) RI (7)
∂z
It is the socalled photophysical model,4547 which is
based on the reasonable assumption that activation R ) σANA + σBNB
energy of thermal decomposition of polymer chains
can be smaller in the electronically excited state than NA + N B ) N 0
in the ground state.
In section V, we consider other “intermediate Here NA and NB are the number densities of A and
models” (i.e., models between pure photochemical and B species, respectively, I is the light intensity, which
pure photothermal). The necessity to develop these is measured in W/cm2, ηA is the quantum yield, σA
models is based, in particular, on recent experimental and σB are the absorption crosssections, and R is the
findings of influence of elevated temperatures on absorption coefficient. This model describes irrevers
photochemistry.4849 ibly induced darkening (for σB > σA) or bleaching (for
Section VI is devoted to the role of mechanical σB < σA). We do not need a differential equation for
stresses in laser ablation. In fact, the importance of NB since the conservation law N0 ) const.
mechanical stresses for laser ablation has been The initial and boundary conditions are
discussed from the beginning of ablation era.50 Me
chanical stresses are caused either by thermoelas NA(z, 0) ) N0, NB(z, 0) ) 0, I(0, t) ) Is(t) (8)
ticity or by chemical changes during polymer modi
fication.5059 As an example, one can refer to an Here Is(t) can be an arbitrary function of time.
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 523
One can consider instead of eq 6 a more general These k1 ordinary equations with conditions
model, which consists of two successive photochemi Sm(S1,0) ) Sm,0 provide the expressions for Sm as a
cal reactions: function of S. Thus, we can introduce
hv hv Sm ) Sm(S)
A 98 B 98 C
Ψ(S) ≡ Ψ1(S,S2(S),...,Sk(S))
In contrast to eq 6, this model can describe a no
monotonous change of the absorption coefficient. R(S) ≡ R(S,S2(S),...,Sk(S)) (15)
The initial and boundary conditions will be of the The boundary condition for intensity is similar to eq
form (eq 8) with the additional condition NC(z,0) ) 8. The general problem (eqs 1618) can be solved
0. analytically. From the first eq 16, we can express
By a similar way, three, four, etc., successive or I ) ∂S/∂t/Ψ(S). Then, the second eq 16 yields:
branching reactions can be taken into account to
describe modification of material. If each step is
caused by the photon absorption, then the kinetic
equations will be of the form:
[
∂ ∂S
∂z ∂t / ∂S
]
Ψ(S) ) R(S) /Ψ(S)
∂t
It results in
∂Sm
∂t
) Ψm(S1,S2,...,Sk)I, m ) 1,...,k (11) [/
∂ ∂S
∂t ∂z
Ψ(S) + ∫S
S R(S′)
0 Ψ(S′)
dS′ ) 0 ] (19)
consists of number densities NA, NB, and NC. The Integrating ordinary differential eq 20 yields the
boundary condition for intensity is similar to eq 8, solution that we present in the form, which is
i.e., I(0,t) ) Is(t), and the initial conditions are convenient for the future:
Sm(z,0) ) Sm,0 ) const, m ) 1,...,k
z  z0 ) ∫S(z)0
(13) S(z ) dS′′
(21)
S′′ R(S′)
Ψ(S′′)∫S dS′
This type of model was used in refs 1619 as well 0 Ψ(S′)
on the integrated dose ∫t0Is(t)dt, see eq 23. It follows is the integrated dose, which come to the point z
from eq 20 that spatial derivative of S at each point before the moment of time t.
within the sample depends only on S; that is, know We chose S ) S h . Now we have Ψ(S h ) ) 1, and all
ing S at the particular point, we know the derivative the formulas become simpler. Sm(S h ) can be found
∂S/∂z. Equation 22 can be expressed in the form: from the set of ordinary equations:
f1(S) ) ∫S
Sfixed dS′′ h0 ) 0
S (32)
S′′ R(S′)
Ψ(S′′)∫S dS′ h (0,t) ) ∫0 Is(t)dt
S
t
(33)
0 Ψ(S′)
h
)  ∫0 R(S
and ∂S h
S
h ′)dS
h′ (34)
∂z
Ω(t) ) ∫S
S(0,t) dS′′ h ′′
dS
z ) ∫Sh
h (0,t)
S
S′′ R(S′) (35)
Ψ(S′′)∫S
fixed
0 Ψ(S′)
dS′
∫0 h ′′
S
h ′)dS
R(S h′
h
∂S Solution of the eqs 37 and 38 is shown in Figure 1.
) I; h (z,0) ) 0
S (28) One can see the propagating wave of photochemical
∂t
modification along the ξ coordinate. As it is explained
According to eq 29 above, this solution describes some universal profile
obeying eq 37 moving with respect to coordinate with
the velocity (eq 39) in such a way that the boundary
h (z,t) ) ∫0 I(z,t)dt
t
S (29) relation (eq 38) holds.
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 525
nB ) 1  nA (40)
dSs(t) ∂S(z,t)
dt
)
∂z 
z)zs
‚
dzs ∂S(z,t)
dt
+
∂t  z)zs
(44)
∂sj
∂ξ
) (β  1)(1  exp( sj))  β sj
∂S(z,t)
∂t z)zs
) Ψ(Ss)Is(t) (45)
{ }
(The FrenkelWilson Approach)
dSs Vetch(Ss,Is)
In this section, we consider the problem of photo ) Ψ(Ss)Is 1  , Ss(0) ) S0 (47)
dt Vmod (Ss,Is)
chemical modification with a moving interface. We
start with the FrenkelWilson approach to this where Vetch(Ss,Is) is given by eq 43, and Vmod (Ss,Is) is
problem. The results can be applied to analysis of given by eq 26:
photochemical etching when photomodified material
is etched due to surface photochemical reaction with Is
surroundings. Vmod (Ss,Is) )  (48)
S0 R(S′)
During etching, a part of the material is removed
from the surface of the sample. As a result, the
∫S
s Ψ(S′)
dS′
problem with the moving interface arises. There are
two approaches to the formulation of this problem. From the above section, it is obvious that the
The first one is similar to the FrenkelWilson ap considered process can be represented as the propa
proach in the theory of melting front propagation.7 gation of the wave of modification and the front of
Within this approach, the ablation velocity is con etching. The etching front propagates with the veloc
sidered as a function of intensity and the values of ity (eq 43), while the modification wave propagates
variables {Si} at the moving interface. This approach with the velocity (eq 48). Generally, Vetch * Vmod. It
for the photochemical theory of UV etching was is important that Ss(t) obeys a closed ordinary dif
developed in ref 37. ferential eq 47. Solving eq 47, one obtains Ss(t).
We consider the model with eqs 11 and 12 and Substituting this function in eq 43, one yields the
moving interface positioned at z ) zs(t). Instead of dependence Vetch ) dzs/dt.
eq 18, we consider the boundary condition of the The coordinate distribution of modification prod
form: ucts in the remaining part of the sample at the
moment t, S(z,t) can be obtained from eq 21:
I(zs,t) ) Is(t) (41)
z  zs ) ∫S (t)
S dS′′
(49)
S0 R(S′)
Ψ(S′′)∫S′′
s
Henceforth, we use the subscript s for surface dS′
values of the variables. Ψ(S′)
526 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
Thus, we reduced the set of partial differential eqs const, etching velocity is proportional to intensity
1113, 41, and 42 into a set of ordinary differential according to eq 51, but the spatial distributions of
eqs 20 and 47. Equation 49 is another form of eq 20. all the {Si} variables will not change in time if we
Thus, the kinetics of photochemical surface etching fix the reference frame with the moving interface.
can be represented as propagation of profiles PSi(ξ)
with the velocity (eq 48) accompanied by propagation D. Single Step Model. Results and Discussion
of the etching front. Ordinary differential equation
Let us apply general formalism to the particular
47 allows one to obtain the surface value of each {Si}
case of model (eq 6). Along with the eqs 7, we
variable involved as a function of time. It allows one
introduce the expression for the surface etching
to build the spatial distribution of each variable at
velocity, assuming its linear dependence on NA and
each moment of time using eq 20 or eq 49.
NB. Thus
Let us consider a particular case when Is ) const.
Here the condition Vetch ) const in time corresponds Vetch ) (GANA + GBNB)Is (54)
to a stationary wave solution and is equivalent to the
condition dSs/dt ) 0, or Ss ) const. This constant,
The problem (eqs 7 and 54 may be rewritten in
let us designate it S/s , obeys the equation: dimensionless variables (eq 36)):
{
Ψ(S/s )Is 1 
Vetch(S/s ,Is)
Vmod (S/s ,Is) } )0
∂nA
∂τ
) nAq;
∂q
∂ξ
) nAq  β(1  nA)q;
dξs
or, in physical cases: ≡ Ṽetch ) ν{nA(ξs) + g[1  nA(ξs)]} (55)
dτ
Vetch(S/s ,Is) ) Vmod(S/s ,Is) (50) ξs(τ ) 0) ) 0; q(ξs) ) 1; nA(ξs ) 0) ) 1
It means that the stationary modification and
Here ξs (τ) is the dimensionless position of the etch
etching waves propagate with the same velocity. As
front. q ) I/Is is the dimensionless intensity, q(ξs),
it is seen from eq 50, S/s generally depends on nA(ξs) are the values of variables at the interface. The
intensity. Because Ss ) const, the spatial distribution discussed problem is characterized by three dimen
of all the {Si} variables will not change in time if we sionless parameters involved: β ) σB/σA; g ) GB/GA;
fix the reference frame with the moving interface. ν ) GAN02/ηA.
This stationary wave solution can serve as an attrac To use mathematical formalism developed in sec
tor, i.e., the solution of the problem can tend to the tion IIC, we assign (see above):
stationary wave.
If etching velocity is proportional to intensity nA ) S, Ψ(S) ) S, S0 ) 1
Vetch(Ss,Is) ) V
h etch(Ss)Is (51)
The dimensionless modification velocity, see (eq 48),
and etching velocity as a function of surface value
then
Ss ≡ nA(ξs) read:
Vetch(Ss,Is) R(S′)
h etch(Ss)∫S
Ss 1
)V dS′ Vmod ) (56)
Vmod (Ss,Is) 0 Ψ(S′) (1  Ss)(1  β)  β log Ss
As a result, eq 47 becomes an equation with Ṽetch ) ν[Ss + g(1  Ss)] (57)
separating variables and can be solved in quadra
tures. Introducing a new time variable (surface dose): Thus, the main eq 47 or 52 becomes:
τs ) ∫0 Is(t)dt
t
dSs
) Ss[νSs + g(1  Ss)][β log Ss 
dτ
one can transfer eq 47 into the following form:
(1  Ss)(1  β) + 1]; Ss(0) ) 1 (58)
dSs
dτs (h etch(Ss)∫S
) Ψ(Ss) 1  V
Ss R(S′)
0 Ψ(S′)
dS′ ; ) This is an ordinary differential equation allowing one
to obtain the dependence Ss(τ). Substituting this
Ss(0) ) S0 (52) solution into (eq 57), one finds the dependence Ṽetch(τ).
Dose dependence of etch depth, he, can be found by
The stationary value S/s obeys the equation (see integrating
eq 50):
R(S′) he(τ) )
1
∫τ Ṽ (τ)dτ
σAN0 0 etch
(59)
Ṽetch(S/s )∫S
S/s
dS′ ) 1 (53)
0 Ψ(S′)
In eq 59, σAN0 is the initial absorption coefficient.
where S/s does not depend on the intensity. Integrated dose (J/cm2) is τ × pω/σAηA. When com
This stationary solution does not propagate with paring with experimental data pω/σAηA also serves
constant velocity with respect to real time if Is(t) * as an important parameter.
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 527
and their use for irradiation of polymers increases According to eq 29, S h (z,t) ) ∫t0 I(z,t)dt is the inte
once again the interest to the theory of laser ablation, grated dose, which comes to the point z before the
where the most intriguing point is the interrelation moment of time t. It means that κph is the number
between thermal and nonthermal processes. From density of photons, which should be absorbed at this
the very beginning of UV laser ablation modeling, it particular point to produce critical number density
was believed that polymer ablation is dominated by of broken bonds at this point.
direct photochemical mainchain scission.10 The com
Ablation velocity (eq 63) coincides exactly with the
prehensive investigations83 have shown, however,
velocity of modification (eq 26). According to section
that, at least for the so largely studied and used
II.D, it means that the spatial distributions of all the
polymer as PMMA, only with VUV the direct photo
{Si} variables will not change in time if we fix the
chemical mainchain scission can be really relevant
reference frame with the moving interface.
to the laser ablation process.
The problem is how to include correctly the modi Let us consider now singlepulse and multipulse
fications and moving interface. It should be noted ablation kinetics within the photochemical ablation
that the Stefantype problem for polymer ablation, model.
when chain scission is a solely thermally activated Equation 63 has been written in the assumption
process, was comprehensively studied in ref 42 and that the number density of broken bonds at the
will be discussed within the next sections. surface corresponds to its critical value. Initially,
Similar to section IIB, we consider the eqs 11 and however, we have no broken bonds at the surface of
12 reduced to eqs 16 and 17 with a moving interface the material.
zs and with a boundary condition (eq 41). Now eq 42 If pulse fluence is not enough to produce the critical
is not valid and the time dependence of ablation number of broken bonds at the surface, then there
velocity
would be no ablation at all. Thus, there is some
dzs threshold fluence Φth, which can be estimated from
V(t) ) (60) the following considerations.
dt
We introduce pulse fluence Φ ) ∫I0dt (for rectan
should be obtained from the Stefanlike condition: gular pulse Φ ) ∫t0p I0(t)dt, where tp is laser pulse
duration). Here I0(t) is the laser intensity. For an
Ss ) Scr ) const (61) immovable interface the nonreflected intensity at the
surface is given by
where the value Scr corresponds to critical value of
the number density of broken bonds. Is(t) ) I0(t)[1  R({Si(t)})] ) I0(t)[1  R(S
h (t))] (66)
Now we once again consider eq 44:
dSs(t) ∂S(x,t)
dt
)
∂x  ‚V(t) +
z)zs
∂S(x,t)
∂t  z)zs
(62)
Here all the values of variables are taken at the
surface.
Combining eqs 28 and 66 easily yields:
From eq 61, it follows that in our case dSs(t)/dt ) 0
h
Φth ) ∫0
and from eq 62 one obtains the expression for the h cr
S dS
(67)
ablation velocity: 1  R(S
h)
 
If Φ > Φth the interface will move according to the
V(t) ) 
∂S(x,t)
∂t /
z)zs
∂S(x,t)
∂x z)zs
)
Scr R(S′)
law (eq 64) during the time tcr < t etp where tcr obeys
the equation ∫t0cr I0(t)dt ) Φth. Since the interface
Is(t)
/∫ S0 Ψ(S′)
dS′ (63)
starts moving, the surface intensity Is(t) will be
connected with I0(t) through the absorption within
the plume. Assuming the simplest model of plume
Equation 63 suggests that, when Scr is fixed, the absorption we can write (for t > tcr):
ablation velocity is proportional to light intensity at
the surface and its dependence on time entirely Is(t) ) (1  R(S
h cr))I0(t) exp(Rph(t)) (68)
follows the time dependence of surface intensity.
Thus, we can write:
Here h(t) ) zs(t) refers to the ablated depth at time
Is(t) t, and RP refers to the Lagrange extinction coefficient
V(t) ) (64) of the plume (extinction coefficient of the plume
pωκph
recalculated per ablated depth). Here we neglect the
possible influence of plume on the reflection coef
Here κph is a constant. To understand the physical
ficient. From eqs 64 and 68, we obtain the ordinary
meaning of this constant, let us make a special choice
differential equation:
of the variable S (see eq 28). Now we have Ψ(S h) )
1 and
dh I0(t) exp(Rph)(1  R(S
h cr))
V) ) ; h(tcr) ) 0
κph ) ∫ R(Sh )dSh
1 Sh cr
pω 0
(65) dt pωκph
(69)
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 529
Integration of eq 69 yields the etch depth, he, per from the logarithmic law, with h tending to zero when
single pulse as a function of laser fluence: Φ f 0. That corresponds qualitatively to the behavior
( )
of the kinetics curve obtained in ref 82 for laser
1 RP(Φ  Φth)(1  R(S
h cr)) ablation of PMMA and Teflon at 125 nm.
he ) ln 1 + (70) For small fluences the kinetics curve predicted by
RP pωκph
eq 71 follows the linear law:
Let us consider several special cases of this
formula. Thus, if reflection coefficient is not practi Φ(1  R(S
h cr))
he = (74)
cally influenced by the modification process, R(S h) ) pωκph
const ) R, then (see eq 67)
or in case (eq 72):
h cr ) Φth(1  R); κph )
S ∫
1 Φth(1  R)
pω 0
R(S
h )dS
h,
Φ
he ) (75)
and if in addition R(S
h ) ) const ) R, then RΦth
( )
RP(Φ  Φth) photochemical reaction. In our case, this transition
1 corresponds to chain breaking with simultaneous
he ) ln 1 +
RP RΦth creation of byproducts, which change the optical
properties of the material. For example, it can be
This equation coincides with the formula obtained direct chain breaking of main polymer chain which
in ref 30. is accompanied by the creation of unsaturated CdC
Let us consider now multiplepulse ablation kinet bonds near the newly developed ends of polymer
ics. If Φ > Φth, then at the end of the first pulse we chain (see, e.g., ref 84). It is known that the chain
have at the boundary S h )S h cr. If Φ < Φth then we breaking process due to irradiation of polymers by
have no ablation at all for the number of pulses less UV and VUV photons is often accompanied by a
or equal to 〈Φth/Φ〉, an integer part of the number significant change of absorption.8486 It can be either
Φth/Φ, (incubation) and then, after the next pulse, we darkening or bleaching. The kinetics of modification
have S h )Sh cr at the boundary. Thus, in both cases caused by eq 6 is addressed by the set of eq 7. We
each pulse, which ordinal number is greater than rewrite this set in an equivalent form.
〈Φth/Φ〉 + 1, will etch absolutely the same depth,
which can be easily found from eq 69 with the initial ∂NB ηAσA
condition h(0) ) 0. This yields the resulting ablated ) (N0  NB)I (76)
depth per such pulse: ∂t pω
( )
∂I
1 RPΦ(1  R(S
h cr)) ) (σBNB + σA(N0  NB))I (77)
he ) ln 1 + (71) ∂z
RP pωκph
Here NB stands for the number density of broken
If one irradiates material with an amount of pulses bonds, N0 being the number density of initial bonds,
much greater than 〈Φth/Φ〉 + 1, then the averaged and N0  NB being the number density of surviving
etch depth per pulse, which usually is calculated as bonds. σA refers to the absorption crosssection of
the resulting depth divided by the number of pulses, initial material recalculated per number density of
can be estimated using eq 71. If R(S h ) ) const ) R initial bonds. σB refers to the absorption crosssection
and R(Sh ) ) const ) R, eq 71 becomes: of products of photochemical reaction recalculated per
( )
number density of broken bonds. ηA stands for the
1 RPΦ quantum yield of photochemical bond scission. NB )
he ) ln 1 + (72)
RP RΦth Ncr stands for the critical number density of broken
bonds providing ablation. We apply the mathematical
The “photochemical law” (eq 1) is often used for approach developed in the previous section. We
interpreting the data on laser ablation kinetics: choose NB as an S variable, S ) NB, then
he )
1
Reff
log
Φ
(
Φapp.th ) (73) Ψ)
ησA
(N  NB); R ) σBNB + σA(N0  NB);
pω 0
Here Using eqs 82 and 16, we can easily find the surface
temperature, Ts, to be
1 1 σB Ncr
[ (
γ̃ ) β ln
δ 1δ
1, β)
σA) ]
and δ )
N0 Ts ) T0 +
1 Scr Λ(S)
∫ dS (83)
cpF S0 Ψ(S)
Equation 71 now looks as follows (if we suppose that
R(NB) ≈ const ) R): Here T0 refers to the ambient temperature and we
put in zero in the following calculations. If we put
he )
1
RP [
ln 1 +
ηARPΦ(1  R)
pωNcr(1 + γ̃) ] (79)
all the enthalpies i equal to zero, then, using
definition of κph we obtain the estimation:
pωκph
For small δ, δ f 0, γ̃ f 0, and κph ≈ Ncr/ηA; Ts ) (84)
therefore, eq 79 for small Φ (eq 74) comes to the cpF
formula of ref 28. However, for real situation δ
appears to be quite close to unity and the effect of It should be noted that estimation eqs 83 and 84
modification is significant. Let us estimate typical are valid for singlepulse ablation. Indeed, while
value of κph. Taking N0 ≈ 6 × 1021 cm3 and δ ) 1/2 temperature relaxes between pulses due to heat
for β ) 1 and η ) 1 we have γ̃ ≈ 1.3 and κph ≈ 4 × diffusion, variables Si assumed to be not relaxing.
1021 cm3 . If β ) 2 and η ) 1 then γ̃ ≈ 1.6 and κph ≈ Let us consider now the case when the heat
5 × 1021 cm3. diffusion is significant. First, we consider stationary
ablation when Is ) const and ablation velocity is also
G. Temperature Estimations constant, V ) const.
The temperature distribution within the moving
To make the photochemical theory of laser ablation reference frame fixed with the ablation front obeys the
selfconsistent, let us estimate the temperature rise, equation:
which will occur at the interface during photochemi
cal ablation.39,40 Really, if this temperature appeared ∂T ∂2T Λ(S)I(z,t) ∂T
to be high enough either to provide thermal destruc ) DT 2 + +V (85)
tion and evaporation of material or to influence
∂t ∂z c pF ∂z
significantly the photochemical process, then it would
follow that the pure photochemical ablation model Here z ) 0 corresponds to the interface. DT is the
is not relevant. Simultaneously, we will estimate the heat diffusivity. It can be checked directly that from
domain of applicability of the above ablation model. eqs 16 and 20 it follows that
Let us start with the single pulse ablation and
∂
perform estimation “from above” of the surface tem Λ(S)I(z,t) )  (F(S)I) (86)
perature provided that we can neglect the heat ∂z
diffusion.
In this case the temperature rise, T, can be where
estimated from the equation:
R(S′)
∂T
)
R(S)I k
 ∑i(S)
Ψi(S)I
(80)
F(S) ) ∫S
S
0
Λ(S′)
Ψ(S′)
dS′
/ ∫SS Ψ(S′)dS′
0
(87)
( )
Here cp refers to the specific heat, and F is the
density of the material. In what follows, for simplic ∂T ∂ ∂T F(S)I(z,t)
) D + + VT (88)
ity, we will regard them as constants. Here Ψi(S) ≡ ∂t ∂z T ∂z cpF
Ψi(S1(S),...,Sn(S)), i(S) being the endothermic effect
of corresponding photochemical transitions. If we With Is ) const and V ) const, the temperature
introduce the function: distribution tends to be stationary (see e.g., ref 25).
Integration of eq 88 yields the corresponding equation
k
for the stationary temperature:
Λ(S) ≡ R(S)  ∑i(S)Ψi(S) (81)
i)1
∂T F(S)I
DT + + VT ) 0 (89)
then (eq 80) becomes: ∂z cpF
Substituting the expression for ablation velocity According to this theory the ablation velocity, after
from eqs 63 and 64 yields ablation starts, is proportional to the light intensity
on the surface, the coefficient of proportionality, κph,
1 Scr Λ(S)
Tst ) ∫
cpF S0 Ψ(S)
dS (91)
being the number density of photons which should
be absorbed at this particular point to produce critical
number density of broken bonds at this point.
Equation 91 coincides with eq 83. It means that For multiplepulse irradiation this model predicts
this estimation is good for singlepulse or well logarithmic dependence of etch depth on laser fluence,
developed ablation. Equation 91 is quite remarkable if fluence is much higher than apparent threshold,
because Tst does not depend on intensity. In fact, and linear dependence for fluences much smaller than
when we speak about the photochemical ablation, we apparent threshold.
assume implicitly that the surface layers are etched
before they are heated to high temperature. Equation Temperature estimations show, however, that sur
91 provides a test for such an assumption. face temperature for single pulse or quasistationary
Let us make some estimations. Consider the ex ablation is small enough only if κph < 1021 cm3.
ample of singlestep model discussed in previous With larger κph pure photochemical ablation can be
section. Here S ) NB, and relevant at fluences higher than apparent threshold
only with large enough plume extinction coefficient.
ηAσA It should be noted, however, than for singlepulse
Ψ) (N0  NB); R ) σBNB + σA(N0  NB),
pω ablation, and for high enough fluences for multiple
pulse ablation, this model can hardly be relevant in
Λ ) σBNB + σA(N0  NB)  η σ (N  NB) ) this pure photochemical variant if there is no physical
pω A A 0
mechanism that makes quantum yield of photochemi
σBNB + σA(N0  NB) 1  ( )
η (92)
pω A
cal bond breaking significantly greater than unity.
It will need consideration of thermally activated
Here is the endothermic effect of photochemical processes. These processes can either influence the
chain scission and accompanying reactions. Temper dark reaction, following the photochemical initiation,
ature elevation can be expressed as: such as depolymerization, or change the character
istic of material removal, affecting, for example, the
Tst )
1 Ncr Λ(NB)
∫
cpF 0 Ψ(NB)
dNB )
κph
cpF
pω  (
ηA
1 + γ̃ ) (93)
critical number density of broken bonds.
and the heat source term Q is given by In the present form, the model contains nonlin
earities and nonstationary effects, which normally
1 ∂I RI can be analyzed by numerical solution with the help
Q) ) (97)
cpF ∂z cpF of the finite element technique.87 With the moment
method technique88 which we will use for analysis,
In this reference frame z ) 0 corresponds to the the given problem can be efficiently reduced to the
position of the interface and convective term V ∂/∂z system of three coupled nonlinear ordinary dif
appears in the righthand site of the equations with ferential equations practically with a very small loss
the time derivative in the lefthand site. in accuracy. Solution of the ordinary differential
The intensity distribution within the material I(z,t) equations, in turn, is appellate to the fast Runge
is governed by the BouguerLambertBeer equa Kutta procedure, which is a routine part of many
tion: mathematical software. Thus, we obtain a fast and
realistic (quantitative) simulation of purely thermal
∂I effects in laser ablation.36
) RI (98)
∂z The idea of the “moments method” or “nonstation
ary averaging” method (see, e.g., ref 88) is close to
Here R is the effective absorption coefficient. Gen Galerkin’s method to find the approximating solution
erally, R should be found from an additional set of of the nonlinear problem. This technique, for ex
equations, but in this section we will treat it as an ample, was successfully applied to solve some prob
independently known value. Equation 98 is consid lems in laser thermochemistry.89 We applied a simi
ered together with the boundary condition lar technique for the analysis of laser ablation
problems. The details of the procedure and examina
I(0,t) ) [1  R(Ts)]I0(t) exp[RPh(t)] (99) tion of the method accuracy for particular cases are
discussed in ref 90.
where I0(t) is input laser intensity, RP is the Lagrange The idea of the moment method is quite simple.
absorption coefficient of the plume, R is reflection The exact solution T ) Tex (z, t) of the boundary value
coefficient (which can depend on the surface temper problem (eq 95102) should identically fulfill eq 92.
ature), and h(t) is the ablated depth We use designation B[T] for the righthand part of
eq 95. Thus,
h(t) ) ∫0 V(t1)dt1
t
(100)
∂Tex
For the energy flux, we employ the boundary cF  B[Tex] ≡ 0 (103)
∂t
condition:7

∂T If we use some other “test function”, i.e., trial
κ ) FV∆Hs (101) solution T ) Tp (z, t), instead of T ) Tex then the
∂z z)0 identity of eq 103 will be broken because of the
Here ∆Hs is a constant that is close to the difference singularity of the Cauchy problem. Nevertheless, we
in enthalpy of solid and gas phases.7 can use the appropriate functions Tp (z, t) for ap
The second boundary condition (at infinity) and proximation solution if we require that this trial
initial condition are obvious: Tzf∞ ) Tt)0 ) T∞. One solution will fulfill the “conservation laws” for the
should use the realistic pulse shape I0(t). For ex moments
ample, for smooth pulse shape of the excimer lasers
dMn
≡ ∫0 dzznB[Tp(z,t)] ) 0, where Mn )
one can use approximation:7 ∞
[ ]
dt
t t
I0(t) ) I0 exp 
tp tp
(102) ∫0∞ dzznH(z,t) (104)
The given problem can be solved numerically, e.g., Here H refers to the enthalpy H(T) ) ∫T0 cp(T1)dT1.
by finite difference technique with temperature The total number of eqs 104 should be equal to total
dependent coefficientssheat capacity, heat conduc number of unknown time dependent functions with
tivity, reflection, absorption coefficient, etc. An effi in the test function Tp (z, t). This procedure corre
cient method to solve this problem by moment’s sponds to minimization of the solution functional
technique was suggested in ref 36. F [Tp (z, t)] along the directions zn within the func
The density of solid should be considered with a tional space. If we will use for the trial solution
good accuracy as F ) const, meanwhile the heat directions of the fastest descent in the functional
capacity c, heat conductivity κ, and the heat source space, the moment method becomes identical to
term Q depend on temperature T. These dependen Galerkin’s method.88
cies can be rather complex. The difference between the Galerkin and moment
Although some simplifications have been done methods refers to physics. There is no general
during the formulation of boundary value problem algorithm how to chose the trial function. Normally,
(eqs 95102) the model is still acceptable for the one chooses the trial solution on the basis of own
quantitative analysis of experimental data, while the experience and intuition. In principle, a majority of
further simplification, typically, leads to a big de trial solutions is acceptable. One should know how
crease in the numerical accuracy of analysis. the fitting functions (unknown functions which one
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 533
ance, while equation for the moment M1 means the where a(t), b(t), and l (t) are some functions of time
local energy balance with respect to some character only. The first term in eq 112 describes the change
istic length l . A number of important parameters and of the enthalpy distribution with a characteristic
desirable conservation laws should be introduced scale, related to absorption of radiation, while the
from the physical sense of the problem. second term describes the changes in the enthalpy
Within the discussed problem we will consider two distribution, related to the heat conduction. The
important parameterssthe surface enthalpy Hs(t) ≡ characteristic length l (t) plays the same role as a
H [Ts (t)] and characteristic length l (t) for the en thermal length within the linear heat equation. The
thalpy distribution. These two quantities yield the amplitudes a and b should be expressed through the
most important information about the distribution surface enthalpy Hs(t) ) Hp(z ) 0,t) with help of
of internal energy within the solid, i.e., we believe boundary condition (eq 108):
[ ]
that this distribution, mainly, control the ablation.
To introduce corresponding moments we first re 1 Vl ∆Hs
a) Hs + ,
write our boundary value problem for the enthalpy 1  Rl DTs
[ ]
H. Thus, eq 95 transforms to
1 Vl ∆Hs
b) Rl Hs + (113)
1  Rl DTs
F[∂H∂t  V∂H
∂z ] ∂z( ∂z ) ∂z
∂ ∂T
) κ
∂I
 . (105)
Thus, our trial solution automatically fulfills all the
Within the righthand part of eq 105 the no trans boundary conditions and we can write the equations
formed functions of the temperature are staying. for unknown functions Hs and l using the moment
According to our consideration we introduce two method. Substitution of eqs 112 and 113 into eq 106
moments yields
1 V
M0(t) ) ∫0 H(z,t)dz and M1(t) ) ∫0 zH(z,t)dz
∞ ∞
(106)
M0 ) 1 +( Rl )
l Hs +
RDTs
l ∆Hs (114)
( ΦB)
h ) A exp  (118)
[ ]
300 K, cp ) 2.551.59 exp[(300  T)/460] J/g K, κ )
1.55 × 103(T/300)0.28 W/cm K, F ) 1.42 g/cm3, ∆Hs ) 500 1 Φ B
h) log , Φp ) . (120)
J/g, Rp ) 0.45 R, λ ) 193 nm (triangles): A ) 0.93, R ) Rp Φp log (RpA)
4.25 × 105 cm1, λ ) 248 nm (circles): A ) 0.88, R ) 3.1 ×
105 cm1, λ ) 308 hm (diamonds): A ) 0.89, R ) 105 m1,
λ ) 351 hm (squares): A ) 0.9, R ) 0.32 × 105 cm1. In Transitions between different regimes can be de
plot (a) maximal temperatures of the surface are shown scribed well by the interpolation formula, which can
(dots). The value of temperature is in a good agreement be presented by inverse function Φ ) Φ(h):92
with measured experimentally.93
Φ ) B exp[Rph]log1[A/h] (121)
this solution describes well all known analytical
solutions, typically, with accuracy 13% during the
period, comparable with interaction time, i.e., up to In Figure 6 one can see these three typical depend
≈35 tp (tp is duration of laser pulse). The late stage ences for the case of excimer laser ablation of poly
of the temperature evolution, t . tp can be described imide as well as interpolation of experimental data13
with less accuracy (≈ 1030%) but this late stage is by eq 121.
not important for the description of ablation. A weak dependence of integral curves on detailed
This solution describes well the influence of the ablation kinetics means that dependencies h ) h(Φ),
temperature dependencies in cp(T), κ(T), and R(T) presented in hundreds of experimental papers, do not
and has a lower accuracy for R(T). Within the yield sufficient information for the establishing of an
presented procedure, the temperature dependence in ablation mechanism. For this analysis, one needs
absorption coefficient is taken into account by sub some additional information. The very informative
stitution R w Rs ) R[Ts]. are data on the dynamics of surface temperature
Calculations with a thermal model, which take into variation, but it is very difficult to measure. Among
account all temperature dependencies of parameters, the few successful examples, we should mention ref
were done in refs 36 and 90. An example of these 93, where the temperature of polyimide surface
calculations is shown in Figure 5 for excimer laser during excimer laser ablation was measured near the
ablation of polyimide. One can see that kinetic curves ablation threshold. Pay attention that this temper
for radiation with 350, 308, and 248 nm are in good ature is in good agreement with calculations in
agreement with the surface photothermal model. At Figure 5.
the same time radiation with 193 nm produces Probably some comment should be made for rela
ablation effect strongly different from the thermal tively small activation energy Ea ) 1.51 eV, used in
model. calculations. This value of the activation energy
One can see that thermal model yields detailed follows from the analysis of ablation kinetics with
description of the process dynamics. The main prob fixed intensity and variable pulse duration.35 This
lem, however, is that experimentalists typically have value corresponds to thermo gravimetric measure
no detailed data on the dynamics of the ablation ment for polyimide decomposition.94 Direct bond
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 535
Neglecting molecularmass distribution of polymer dent intensity I0 and ablation velocity V) is prereq
chains immediately yields eq 96 in which uisite for further studies. Its consideration for surface
models allows one to understand many features of
Ea ) Em/ns (124) the laser ablation of metals. In general, stationary
Here ns is the surface value ns(t) ) nB(0, t). Em velocity of the interface is determined by the energy
stands for the energy of weak bonds per “monomer”. conservation, and temperature is such, that Arrhe
Monomer here means the molecular group between nius reaction rate is fast enough to maintain this
neighboringalongthechain bonds, which can be velocity. As a result, velocity is about linear with
broken. The expression for ablation velocity now intensity, while (surface) temperature depends loga
reads: rithmically on I in almost every thermal model.
Subsequent mathematical analysis reveals, however,
V ) V0m exp(Em/kBnsTs) (125) some differences between the surface and volume
models.
Within the approach investigated in this paper we, Below we consider stationary ablation within the
following refs 43 and 44, employ the equation for model of section IIIC with zero reaction enthalpy
ablation velocity (3.30) together with the boundary ∆Hb ) 0 and with temperature independent param
condition: eters as it has been done in ref 41. Generalization of
κ(T)
∂T

∂z z)0
) F∆HmV (126)
this analysis can be found in ref 42.
It is convenient to introduce along with nA and nB
the variable b:
Here ∆Hm stands for the enthalpy of evaporation
of weak bonds per “monomer”. The boundary condi
tions for infinity are obvious, as usual
b ≡ log (1  nB) ≡ log ( )
1
nA
(130)

was employed instead of eq 125. The ablation starts
∂T
when the fraction of broken bonds at the surface ) 0; T(∞) ) T∞; b(∞) ) 0 (134)
reaches a certain critical value, ncr. The position of ∂z z)0
the interface thereafter is fixed with this critical
number, i.e., the boundary condition reads: I(0,t) ) I0(t) (135)
ns ) ncr (128) b(0,t) ) log (1  ncr) (136)
This relation defines the position of the interface,
Here DT is the heat diffusivity. For stationary
and therefore the velocity V, implicitly. Stefanlike
solution, we take the solutions that correspond to the
condition (eq 128) can be considered as an ap
constant light intensity I0 and propagate with the
proximation of eq 125 with very sharp dependence
constant velocity V ) const. The stationary wave
of velocity on fraction of broken bonds at the surface.
solution obeys the eqs 131136 with all the time
Another physical meaning of eq 128 can be explained
derivatives being taken to be zero. In what follows,
as follows. The interaction of polymer chains can
we take T∞ ) 0.
proceed also through topological constrictions, en
It is easy to find the first integral for stationary
tanglements. There is an averaged number of mono
solutions (see section IIF). Thus, instead of eqs 131
mers between the neighbor entanglements, ncr, along
and 132 we can write:
the chain. If the length of the chain at the surface
becomes shorter than this ncr and if Em can be ∂T I
neglected, we immediately come to the condition (eq DT ) VT (137)
∂z cpF
128). In this case enthalpy of evaporation also can
be neglected and the boundary condition for the
Equations 133137 yield:
temperature can be written as follows:
κ(T)
∂T

∂z z)0
)0 (129) V log
1
1  ncr
) k0∫0 exp 
∞
(
Eb
kBT(z) )
dz (138)
D. Stationary Wave Solution in Stefanlike Model The integral in the righthand side of eq 138 can
In laser ablation, the understanding of the station be estimated using the saddle point method. It uses
ary regime of material removal (with constant inci Taylor expansion of T near the surface under the
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 537
l T2 ≡ 2Ts
/
∂2T
∂z2
 z)0
(140)
( )( ) ( )
into the enthalpy of decomposition reaction. In the
k0 2/3 TsDTπ 1/3 2Eb conduction region, the reaction rate is small and
V) exp  (143)
1 2TbR 3kBTs absorption is balanced by changes in temperature.
log
1  ncr The size of reaction region (for high velocities) is on
the order of 1/R.
Equations 141 and 143 provide a closed set to The smoothening of temperature distribution near
determine the ablation velocity. This set is much the surface compared to the surface evaporation
similar to that corresponding to a stationary wave model is an important feature of a bulk model. As it
in a simple laser surface evaporation problem. There, is known the temperature distribution near the
along with eq 141 one has the velocity equation in surface in surface evaporation wave has a maximum
the form, see eq 96: beneath the surface. The existence of this maximum
is the reason for instability of a plain surface evapo
V ) V0 exp  ( Ea
kBTs ) (144)
ration wave.25 The absence of such a maximum in a
bulk model results in the absence of the reason for
instability. That is a bulk model predicts more stable
Equation 143 can be approximately represented in ablation than a surface model.
the form similar to eq 144 Let us consider chemical reaction scheme
( )
E a′ AfBfC (146)
V ) V ′0 exp  (145)
kBTs The second channel: B f C can be interpreted as
production of hardablated material C such as “glassy”
The comparison of eq 144 and 145 leads us to the carbon investigated in ref 96. The set of equations
conclusion that a stationary wave in considered A f describing the chain of reactions of eq 146, will
B ablation model is similar to the stationary laser contain eqs 131135 and 128 completed by the
surface evaporation wave with the activation energy equation for fraction of species B (which we will
which is about twothirds of the reaction activation associate as previously with broken bonds)
energy, i.e., in eq 145 E′a ) 2Eb/3.
More rigorous analysis taking into account tem ∂nB ∂nB
)V + nAk0 exp(Eb/kBT) 
perature dependence of heat conductivity and specific ∂t ∂z
heat and, what is more important, ∆Hb * 0 (see ref nBk1 exp(Ec/kBT) (147)
42) shows that the expression of stationary velocity
on surface temperature in the form eq 145 remains and for fraction of species A
with E′a slowly dependent on intensity changing
from E′a ) 2Eb/3 at small intensities to E′a ) Eb at ∂nA ∂nA
high intensities. )V  nAk0 exp(Eb/kBT) (148)
∂t ∂z
One can see that for stationary regime surface
evaporation model resembles the model under study In ref 41, we discussed properties of stationary
in several respects. It is not, however, its limiting wave solutions of the model A f B f C without
case. In particular, it can be shown that in the volume taking into account the enthalpies of reactions eqs
model maximum of temperature is always reached 131135, 147, and 148.
at the surface. Instead of formation of subsurface It can be seen in Figure 8 (curve 1) that if the
temperature maximum observed in surface models,25 activation energy of the bond breaking, Eb, is smaller
the temperature distribution near the surface flattens than the activation energy of the following modifica
538 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
b′′(z ) 0, tcr)z2
∆t )  (150)
2ḃ(z ) 0, tcr)
x
2ḃ(z ) 0, tcr)
h(t) ) U0(t  tcr)1/2, U0 ) 
b′′(z ) 0, tcr)
(151)
Here U0 ) const and can be estimated as follows;
see details in ref 42:
( 2DT
)
1/2
U0 ≈ (152)
exp(R2DTtcr)/erfcxR2DTtcr  1 Figure 12. Dynamics of laser ablation for rectangular
pulse. Absorption by plume is absent. Pulse fluence is
Square root dependence in eq 151 leads to an significantly above the threshold. (a) surface model I, (b)
Stefanlike model II, (c) bulk model III. (Reprinted with
infinite velocity at the initial moment (explosive onset permission from ref 44. Copyright 2002 American Institute
of ablation): of Physics).
U0
V) . (153)
2(t  tcr)1/2
pulse near threshold total ablated depth and the This relation is valid after ablation starts. Codes
threshold fluence. Near the threshold, ablation does used for calculations in this section can be down
not influence the temperature and the reaction rate. loaded from the site http://www.iapras.ru/structure/
Therefore, one can assume, that the profile b(z), optics/div330/lab332/reslines.asp.
which is parabolic near z ) 0: First we compare ablation kinetics, i.e., the depen
dence of ablated depth on fluence per pulse. We
b(z) ≈ (bcr + ∆b)(1  z2/l k2(tm)) (154) consider the experimental data on massloss kinetics
of polyimide irradiated by KrF excimer laser.13 These
is created near t ≈ tm when the reaction rate has a data demonstrate “Arrhenius tails” near ablation
sharp maximum. Here tm is the moment of time when threshold. Bulk models II and III cannot explain
the surface temperature has its maximum, lk is these tails, if we assume layerbylayer ablation as
introduced in eq 140. Afterward, material with the only reason for massloss. However, it has been
b(z) > bcr is ablated. Therefore, total ablated depth understood in refs 101 and 42 that these tails
per pulse he ) h (t ) ∞) is: originate from the depletion of volatile species. These
[ ]
volatile species result from the same bulk reaction
∆b 1/2
he ≈ l k(tm) (155) A f B. This reaction breaks the bonds, destroys
bcr polymer chains, and may simultaneously create
trapped volatile species. Below ablation threshold,
To relate he to the parameters of the laser pulse, the volatile species result in a mass loss, which
one can apply the saddle point method near tm, which requires outdiffusion of trapped species and occurs
yields42 on the microsecond or even millisecond time scale.
( )
As volatile species and broken bonds are produced
Φ  Φth 1/2
in a pyrolytic reaction, this results in an Arrhenius
he ≈ (156) tail. Above the threshold, the volatile species leave
Φth
the material together with the ablation products.
When ablation ceases some of the volatile species still
F. Kinetics and Dynamics of Ablation. Depletion exist below the surface and leave the material later.
of Species and Real Ablation This results in an additional mass loss, M (per unit
In this section, we compare predictions of different area), which does not contribute necessarily to the
photothermal models regarding kinetics and dynam ablated (crater) depth. The above picture is not in
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 541
( )
case can occur at fluence which is smaller than that
pω n2 n3
needed for avalanche or stepwise ionization develop Q) + 
ment. Fcp(T) t21 t32
With ultrashort laser pulses, we cannot employ ∆HbN0(1  nB)k0 exp(Eb/kBT)
equation of section III with R ) const. We have to (163)
cpF
consider the transient response of a media. We shall
assume that radiation is absorbed in a material by For surface photothermal model we should take eq
chromophore groups (chromophores),95 i.e., that the 163 with k0 ) 0. In numerical calculations below, we
first electronic transition occurs in a bound state, consider Gaussian USLP with pulse duration 500 fs.
which is typical of polymers. Since an important
feature of such a response is the saturation of energy B. Kinetics of Single and TwoUSLP Ablation
levels, the absorption of radiation in a dielectric will
be described by multilevel models of this medium and The dependence of ablated depth on laser fluence
we shall take into account stimulated emission and predicted by both surface photothermal model I and
nonradiative relaxation. A set of rate equations for bulk photothermal model III of the previous section
the populations of the energy levels within the three III is studied in ref 44. The characteristic features
level model shown in Figure 15 reads: are as follows:
(i) The bulk ablation starts sharply when fluence
∂n1 ∂n1 σ12 n2 approaches the threshold value, whereas the surface
)V  I(n1  n2) + (159) ablation exhibits Arrhenius tail near ablation thresh
∂t ∂z pω t21 old.
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 543
( ) ( )
with a variable delay time, td, between them. Zero
delay corresponds to the impact of a single pulse with Φ 2 1 Ea
( )
h = tDTV = 8 DT V0 exp 
doubled energy. The effect of two successive USLP pωn0 n0pω
can be characterized by the dependence of the thick kB T∞ +
2cpF
ness of the ablated layer, h, on the delay time td
between these pulses. Hereafter this dependence, (164)
h(td), will be referred to as delay curve. Experimen
tally, this curve has been obtained for polyimide in If we choose values of the parameters close to those
ref 107; theoretically, for a surface photothermal of polyimide: F ) 1.42g/cm3, cp ) 2J/gK, n0 ) 6 ×
model, it has been analyzed in refs 112 and 113. 1021 cm3, R ) σ12n0 ) 3 × 105 cm1, Ea ) 1.5 eV,
Following ref 107, we consider the situation when V0 ) 106 cm/s and take pω = 5 eV (KrF laser) and
laser fluence of one single pulse is smaller than the Φ = 50 mJ/cm2 , we obtain h ∼ 4 nm whereas l s ∼
ablation threshold, whereas the fluence of a doubled 100 nm. That is h , l s. When two successive laser
pulse (zero delay between the pulses) exceeds the pulses each of fluence Φ/2 are applied, the Tmax
threshold. In this case, ablation starts after the end increases (approximately two times if td > tp), whereas
of the second pulse. In the qualitative analysis given the length scale l s decreases. The resultant etch
below, we shall assume, to be specific, that (unless depth h appears to be closer to the length scale l s
otherwise stated) ultrashort pulses bleach effectively and is larger than the etch depth for a single pulse
the investigated medium. Such bleaching, in turn, of double fluence. This means that the consideration
results in different localization of the absorbed energy based on comparison of light penetration lengths does
of two ultrashort pulses with different delays between not work here because the material is insufficiently
them when the delay time is less than a character heated. In what follows this kind of behavior of the
istic heatdiffusion time. The medium is heated after delay curve will be referred to as the regime of
the relaxation of all the electronically excited states. insufficient heating. In this regime, the larger ablated
It is important that an increase in the delay between depth corresponds to a higher surface temperature
two USLPs reduces the saturation of the levels, since but not to the larger penetration depth. Because h
some of electrons drop from an electronically excited according to eq 164 is proportional to Φ 2, whereas
state to the ground state before the arrival of the l s ∝ Φ, with increasing Φh will tend to l s. In this
second pulse. case, the ablated depth provided by a big single pulse
Let us compare the temperature distributions will be close to the l s and larger than ablated depth
(Figure 16) created by the effect of one doubled pulse provided by two Φ/2 pulses. Here the difference in l s
(zero delay between the pulses) and by two pulses plays a crucial role.
with a delay exceeding the electronic relaxation time Thus, it seems natural to consider two regimes of
in the medium neglecting heat diffusion. These laser ablation by ultrashort pulses.44,112,113
distributions are characterized by two important (i) Regime with a characteristic heating scale, when
parameters: the characteristic spatial scale of the the thickness of the removed layer is governed by the
heated region and the surface temperature. The thickness of the heated region of the material, i.e.,
region heated by one doubled pulse is larger than the ablation is faster than heat diffusion;
that produced by the effect of two pulses, but the (ii) Regime with insufficient heating, when the
surface temperature in this case is lower. One can thickness of the removed layer is governed by the
544 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
Experiments on kinetics of laser ablation by nano laxation time. We compare predictions of photophysi
second pulses fail to recognize the mechanism of cal and pure photothermal models to understand the
ablation. In ref 42 (section IIICE) it was argued that possibility to recognize the photophysical effects.
the dynamics of nanosecond ablation differs drasti We consider the effect of USLP on a dielectric,
cally for the surface and the bulk ablation. Within which can be described as a twolevel media. The
the present section following ref 44, we show that a laser frequency is assumed to be in resonance with
more realistic formulation of the bulk model (section the electronic transition. We take into consideration
IIIB) smoothens the singularities inherent to the that the excited level has a complicated structure,
Stefanlike model. It leads to the statement that with thus the effective bandwidth is larger than the
nanosecond pulses, such factors as deviation from bandwidth of the laser radiation. We assume also
sharp rectangular time shape of the pulse, when that the excited electron changes its energy inside
considering ablation dynamics near ablation thresh the level in such a way that the transition frequency
old, as well as plume shielding of the incoming leaves resonance faster than the pulse duration.
radiation for abovethreshold ablation, can make it Thus, we will not take into account the induced
questionable to distinguish between the mechanisms, radiation. This approximation is not very important
for example, with parameters close to those of poly and is made only for the sake of simplicity. We
imide. With subpicosecond pulses, we show that the consider laser ablation of such a media within the
investigation of twopulse ablation kinetics provides framework of a surface evaporation model to compare
information on actual thermal relaxation time almost the predictions of surface photothermal and photo
independently of the mechanisms of ablation. Having physical models.
this information, one can interpret data on delay time Both of the models describe the material response
between the end of a single laser pulse and the start in a similar way:
of the removal of the material from the surface. In
fact, whereas this delay time for the surface model ∂n* ∂n* Iσ12 n*
is close to the thermal relaxation time, the delay time )V + (n0  n*)  (165)
∂t ∂z pω t21
for the bulk model can be significantly longer because
this time is the time of photothermal reaction provid
ing scission of polymer chains. Thus, a combination ∂I
) Iσ12(n0  n*) (166)
of twopulse and singlepulse ablation experiments ∂z
with subpicosecond laser pulses provides a way to
1 n*
distinguish between the mechanisms.
The start of ablation can be fixed, for example,
∂T
∂t
∂T
)V +
∂
∂z cp(T)F ∂z
κ(T)
∂T
∂z
+ [
t21Fcp(T) ]
(167)
using a pumpprobe technique.115117 The only exist
ing data of relevant timeresolved experiments have with the initial and boundary conditions
been published in ref 107. Twopulse ablation experi
ments on subpicosecond ablation of polyimide at 248 n*t)0 ) 0, Tt)0 ) T∞ (168)
nm provided estimation of thermal relaxation time
of about 3050 ps. It was mentioned, however,107 that Iz)0 ) I0(t), n*zf∞ ) 0, Tzf∞ ) T∞ (169)
within time interval of 200 ps after a single 500 fs
pulse with fluence above the ablation threshold there
was no evidence of material removal from the surface. Here I is laser intensity, T is the temperature, n0
From the above analysis, it can be treated as an is the number density of the absorbing groups, n* is
argument in favor of the bulk model. It should be the number density of excited species, ω is the laser
noted, however, that additional experiments are and electronic transition frequency, and σ12 is the
needed. corresponding absorption crosssection. V is the abla
tion velocity. The coordinate system is fixed with the
D. Photophysical Ablation ablation front. t21 is the thermal relaxation time. κ(T)
is thermal conductivity, and cp(T) is specific heat.
Photophysical model of laser ablation has been The difference of photophysical surface model with
suggested in refs 4547. The main idea is that the a surface photothermal model takes place in relation
activation energy for destruction and elimination to the velocity of ablation front and in boundary
from the surface of electronically excited molecules condition for temperature:
is smaller than the activation energy for the mol
ecules in the ground state. Despite the obvious
physical reasons, up to now there is no direct
evidence that the photophysical mechanism really
V) 1
n/s
n0 0 ( )
V exp(Ea/kBTs) +
( )
second harmonic. This can be interpreted as a pho
tophysical ablation.)
The aim of the present communication is to inves
κ
∂T
∂z  z)0
) 1
n/s
n0
F∆HsV0 exp( Ea/kBTs) +
tigate the features of photophysical ablation when the n/s
material is irradiated by USLP with pulse duration F∆H/s V/0 exp( E*/kBTs) (171)
significantly shorter than the electronic energy re n0
546 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
Some ideas about how to combine photothermal chemical FrenkelWilson model considered in section
and photochemical reaction in the theory of laser II. Thus, all the formulas obtained in section II can
ablation have been proposed in refs 120122. We be applied for the analysis of the model eqs 173180.
could formulate these approaches as follows. Up to this point, we have been considering only
The bulk reactions leading to ablation are photo random chain scission mechanism as a chemical
chemical, whereas the elimination of the products of pathway leading to ablation. Very intriguing is the
these reactions from the surface is driven by tem unzipping mechanism of laser ablation. Unzipping
perature. is the process of depolymerization initiated by the
The second idea is that the quantum yield of creation of the radical at the end of the polymer
photochemical bond breaking can depend on temper chain. It is the main pathway of pyrolytic degradation
ature. This is in agreement with the experimental of several addition polymers, i.e., polymers, which are
findings of change in the yield of photochemical obtained by polymerization, such as poly (tetrafluo
reaction of dye molecules incorporated in the PMMA roethylene), poly (methyl methacrylate), poly (R
matrix.48,49 Of course, the mechanism of this change methyl styrene).
is not fully understood at the moment, but one of the Numerous experimental data on plume composi
possible driving forces could be elevated temperature. tion and pulse laser deposition of above addition
As an example, we can formulate one of the polymers indicate that depolymerization is the main
possible models within the proposed approach and pathway in UV laser ablation of these polymers,124130
within the general approach developed in previous because of high content of monomer in the plume.
sections as follows. Moreover, it was shown in ref 130 that even those
Thus, we consider A f B chainbreaking model. addition polymers that pyrolyze by random scission
Chain scission originates from both photothermal and producing little or no monomers provide high mono
photochemical processes. We assume a temperature mer yield being ablated by UV lasers.
dependent quantum yield of photochemical reaction. It is now accepted by all the groups that study laser
For a moving interface, we accept the FrenkelWilson ablation of such polymers that initial chain scission
approach considered in section III. and creation of radicals is provided photochemically,
All the designations are from sections III and IV. while radical depolymerization is driven by elevated
temperature, i.e., photothermallty, because heating
1
∂T
∂t
∂T
)V +
∂
∂z Fcp(T) ∂z
κ(T)
∂T
∂z [
+Q ] (173) of the polymer is also provided by laser light. Thus,
unzipping is one of the remarkable examples of
combined photochemical and photothermal mecha
∂nB ∂nB I nisms.
)V + σAηA(T)(1  nB) +
∂t ∂z pω
(1  nB)k0 exp(Eb/kBT) (174) VI. The Role of Mechanical Stresses
Mechanical stresses caused by laser irradiation of
RI ∆HphotoN0(1  nB)σAηA(T)I
Q)   polymers can strongly influence laser ablation of
cpF cpFpω theses materials. Some authors consider mechanical
∆HbN0(1  nB)k0 exp(Eb/kBT) stresses among the main driving forces of laser
(175) ablation of PMMA.50,53,56,131,132 Specially designed
cpF
photosensitive polymers are reported to be ablated
∂I through “explosive decomposition”.133 It means that
) RI (176) here mechanical stresses play an important role.
∂z
The relevant stresses can be caused by different
R ) σAN0(1  nB) + σBN0nB (177) reasons. They can be thermoelastic stresses, emerg
ing due to thermal expansion. They can also be
V ) V0m exp(Em/kBnsTs) (178) provided by lowmolecular products of both photo

∂T chemical and photothermal bulk reactions. These
κ(T) ) F∆HmV (179) species can result in quasistationary stress due to the
∂z z)0 increase of total molecular volume. The wellknown
Tzf∞ ) T∞, nBzf∞ ) 0 (180) example is depolymerization of PMMA. Polymeriza
tion of PMMA is accompanied by up to 20% of volume
The case k0 ) 0 corresponds to a pure photochemi contraction.134 It means that depolymerization should
cal model with a temperaturedependent quantum be accompanied by extension. On the other hand, the
yield ηA(T). This dependence can obey Arrhenius small, light, fragments, volatile species, consisting of
law.123 This can be recognized as bulk photophysical simple molecules such as CO, CN, CH2, etc., of
reaction (see section IVD). Indeed, if an electronically number density Nl may be treated as an ideal gas,
excited state with the time of life t21 can provide chain which causes an average inner pressure
scission due to thermally activated process with
activation energy E*, then ηA(T) ∝ t21 × exp(E*/ p ) ζ Nl kBT (181)
kBT). Note that similar to our bulk photothermal
model considered in section III the ablation velocity with ζ <1 (only a fraction of the total number of these
depends on both surface temperature and fraction of species will contribute to p).
broken bonds on the surface. It is worth noting that In the simplest case of uniaxial acoustic approxi
if we neglect the heat then we return to the photo mation when only stress tensor component σzz is
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 549
relevant, the equation of thermoelasticity reads: V ) V0m exp(γβN0) exp( Em/kBnsTs) (189)
solved together with the boundary conditions Tzf∞ ) T∞, nBzf∞ ) 0 (193)
σzz(t,z ) 0) ) p(t,z ) 0), σzz(t,z ) ∞) ) 0 (183)
For short pulses when tp < 1/Rcs (for ultrashort
Here p is the quasistationary pressure, which for laser pulses considered in section IV, we should take
the case of volatile species obeys eq 181. here thermal relaxation time rather than pulse
Stress can influence both the bulk photothermal duration) nonstationary effects, caused by transient
bond breaking and material removal from the surface stresses are relevant. These stresses can result in
due to change in the corresponding activation ener spallation, i.e., in the removal of a part of material
gies. A simple estimation of this influence is provided due to propagation of rarefaction wave, as it was
by Zhurkov’s formula (see e.g., ref 94), which reads demonstrated in ref 56, where the film of PMMA as
that decrement of activation energy is linear with a whole was removed from substrate by such a way.
respect to stress. For example, in the case of a simple Transient stresses also can provide bulk chain
photothermal model we can write degradation. Some possible nonstationary effects
when photophysical phenomena are accompanied by
Ea(σ) ) Ea  γσ (184) transient stresses are considered in refs 57 and 58.
Some possible effects of recoil pressure on generation
Eb(σ) ) Eb  γσ (185) of broken bonds were also discussed there.
When examining the bulk photothermal model in
In polymers, γ can have values up to 1021 cm3 (for the form studied in sections III and IV and applying
PMMA γ ) 1.7 × 1021 cm3 94). Equation 185 is valid it to specific materials, estimations should be per
for tensile stress, i.e., when σ > 0. In the opposite formed whether the effect of stresses is significant
case of compressive stress relation (eq 185) is not or not. For example, it was shown in ref 136 that for
obvious, but a decrease in the activation energy of polyimide near ablation threshold both nonstationary
chain breaking is also possible due to local plastic thermoelastic stresses and quasistationary stresses
deformations.135 resulting from pressure provided by heated volatile
Both eqs 184 and 185 are valid only if E > γσ. In species, can be neglected from the point of chain
the opposite case, the chain breaking process will scission if γ < 3 × 1021 cm3 and βm < 0.1.
proceed independently of temperature with preexpo With PMMA there is, as pointed out by several
nential frequency. If Ea < γσ, then the “sublimation” authors,131,137 a contradiction between data on pho
boundary condition is not valid. The particles will tochemical modification with fluencies well below
leave surface with sound and super sound velocities ablation threshold and near ablation threshold. With
and gaskinetics consideration should be applied. small laser fluencies or when PMMA is irradiated by
As an example, let us consider the simple bulk UV lamps there are a lot of evidences published that
photothermal model in quasistationary case, when UV photon being absorbed by ester group (this is a
transient stresses can be neglected. Typically, it is side group on PMMA main chain) results in cleavage
valid if pulse duration, tp, is large enough: tp > 1/Rcs. of this group with small (∼0.01) quantum yield of the
Here R is absorption coefficient and cs is the sound main chain scission.14,77,138,139 The data of authors of
velocity. We assume that the bulk photothermal refs 131 and 137 on modification of PMMA by laser
reaction along with chain breaking process produces pulses with fluences close to the ablation threshold
also m volatile species and introduce βm ) ζm. allow these authors to point out that the chain
scission process initializing depolymerization is much
1
∂T
∂t
∂T
)V +
∂
∂z Fcp(T) ∂z
κ(T)
∂T
∂z
+Q [ ] (186) more effective. One possible explanation of this
phenomenon is that inner mechanical stresses origi
nated from both the extraction of unzipped monomers
∂nB ∂nB and the creation of volatile species during cleavage
)V +
∂t ∂z of side ester group together with heating provided
(1  nB)k0 exp(γβnBN0) exp( Eb/kBT) (187) by laser irradiation can influence, increase, the
quantum yield of photochemical chain breaking.
RI Moreover, the activation energy of the initial pure
Q) 
cpF thermal chain breaking process can decrease due to
( )
γβnBN0kBT arising mechanical stresses also facilitating creation
∆Hb 1  N0(1  nB)k0 exp(Eb/kBT) of the end radicals initiating the unzipping process.
Eb Up to now, we considered some averaged macro
cpF stresses. But at the moment of emerging of monomer
(188) during unzipping or at the moment of cleavage of a
550 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
particular side group and escape of volatile species, the complexity of the discussed problem, this “step
the occurring microstresses can be large enough to by step” approach seems to be constructive.
provide some chemical changing of adjacent mol The modeling of laser ablation of polymers is yet
ecules. Molecular dynamic simulations of some of far from its completion. Nevertheless, some conclu
these processes are performed in papers.50,59 sions can be drawn. First, the etch kinetic curve, i.e.,
There is another interesting problem connected the dependence of etch depth versus laser fluence,
with the influence of stresses, namely, ablation in the being the most popular objective of experimental
presence of outer stresses.140143 Here ablation is works, is not sensitive to the mechanism of ablation.
unstable resulting in surface pattering and cracks Fitting of these experimental data by one or another
formation. theoretical model is not an argument that this
particular model really works. It is only a necessary
VII. Conclusions but not sufficient condition. More informative are
data on dynamics of laser ablation and on surface
Laser ablation of polymers is closely related to temperature.
chemical degradation of polymers caused by laser No doubt that more complex numerical experi
irradiation. The existing knowledge on both photo ments also can be performed to establish agreement
chemical and thermal degradation and stabilization between the theory and experiment.
of polymers could be taken into account as a chemical
background when modeling this phenomenon. How VIII. Acknowledgment
ever, UV laser irradiation provides conditions within
the materials which significantly differ from those The authors express their appreciation to Prof. S.
of usual experiments either pyrolytic or photochemi Anisimov, Prof. D. Bäuerle, Dr. N. Arnold, Dr. M. C.
cal. Castex, Dr. A. Malyshev, Dr. S. Georgiou, and Dr. T.
This is connected with relatively high power den Lippert for many discussions. Part of this work was
sity of irradiation by short, nanosecond, picosecond, done under support of the Russian Foundation for
and even femtosecond, pulses. Using these short laser Basic Research (Grants No. 010216136 and No. 02
pulses, one can create a very high temperature within 0217745).
a very small volume of polymer. These temperatures
simply cannot be reached with conventional tech IX. References
niques, because polymers do not exist at such tem (1) Srinivasan, R.; MayneBanton, V. Appl. Phys. Lett. 1982, 41, 576.
peratures for a relatively long time. High laser (2) Kawamura, Y.; Toyoda, K.; Namba, S. Appl. Phys. Lett. 1982,
40, 374.
intensity also allows creation of numerous electroni (3) Srinivasan, R.; Braren, B. Chem. Rev. 1989, 89, 1303.
cally excited species, high mechanical pressure, and (4) Miller, J. C.; Haglung, R., Jr., Eds. Laser Ablation  Mechanisms
some other effects, which can result in change of and Applications; SpringerVerlag: Berlin, 1991.
(5) Fogarassy, E.; Lazare, S. Laser Ablation of Electronic Materials
chemical pathways.  Basic Mechanisms and Applications; Elsevier: Amsterdam,
Physics of lasermatter interactions, on the other 1992.
(6) Lazare, S.; Granier, V. Laser Chem. 1989, 10, 25.
hand, has much experience with laser ablation and (7) Bäuerle, D. Laser Processing and Chemistry, 3rd ed; Springer
modification of nonpolymeric materials. Our ap Verlag: Berlin, 2000.
proach is to incorporate, as far as it is possible, the (8) Andrew, J. E.; Dyer, P. E.; Forster, D.; Key, P. H. Appl. Phys.
Lett. 1983, 43, 717.
specific features of polymers within the framework (9) Deutsch, T. F.; Geis, M. W. J. Appl. Phys. 1983, 54, 7201.
of models that have been developed for other materi (10) Jellinek, H. H. G.; Srinivasan, R. J. Phys. Chem. 1984, 88, 3048.
als. (11) Dijkkamp, D.; Gozdz, A. S.; Venkatesan, T.; Wu, X. D. Phys. Rev.
Lett. 1987, 58, 2142.
Among the features that should be taken into (12) Oldershaw, G. A. Chem. Phys. Lett. 1991, 186, 23.
account we can mention, for example, the electronic (13) Küper, S.; Brannon, J.; Brannon, K. Appl. Phys. A 1993, 56, 43.
(14) Küper, S.; Stuke, M. Appl. Phys. A 1989, 49, 211.
structure of polymers. In the majority of polymers, (15) Pettit, G. H.; Sauerbrey, R. Appl. Phys. Lett. 1991, 58, 793.
UV photons are absorbed by chromophores in which (16) Pettit, G. H.; Sauerbrey, R. Appl. Phys. A 1993, 56, 51.
several first levels of electronic excitation belong to (17) Pettit, G. H.; Ediger, M. N.; Hahn, D. W.; Brinson, B. E.;
Sauerbrey, R. Appl. Phys. A 1994, 58, 573.
the bound states. (18) Lippert, T.; Bennett, L. S.; Nakamura, T.; Niino, H.; Ouchi, A.;
Another specific feature is a hierarchy of bonds Yabe, A. Appl. Phys. A 1996, 63, 257.
(19) Mansour, N.; Ghaleh, K. J. Appl. Phys. A 2002, 74, 63.
between neighboring molecular groups, namely, (20) D’Couto, G. C.; Babu, S. V. J. Appl. Phys. 1994, 76, 3052.
strong, covalent bonds within a polymer chain and (21) Cain, S. R.; Burns, F. C.; Otis, C. E. J. Appl. Phys. 1992, 71,
relatively weak molecular bonds between neighbor 4107.
(22) Cain, S. R.; Burns, F. C.; Otis, C. E.; Braren, B. J. Appl. Phys.
molecular groups that belong to different chains. 1993, 72, 5172.
One more important point is that chemical reac (23) Cain, S. R. J. Phys. Chem. 1993, 97, 7572.
(24) Masubuchi, T.; Tada, T.; Nomura, E.; Hatanaka, K.; Fukumura,
tions in polymer materials are often accompanied by H.; Masuhara, H. J. Phys. Chem. A 2002, 106, 2180.
the creation of lowmolecular, volatile, species. This (25) Anisimov, S. I.; Imas, Ya. A.; Romanov, G. S.; Khodyko, Yu. V.
is of importance if we take into account that amor Action of HighPower Radiation on Metal; National Technical
Information Service, Springfield, Virginia, 1971.
phous polymer solids generally contain a significant (26) Keyes, T.; Clarke, R. H.; Isner, J. M. J. Phys. Chem. 1985, 89,
amount of free volume. These features have a con 4194.
siderable influence upon laser ablation of polymers. (27) Sutcliffe, E.; Srinivasan, R. J. Appl. Phys. 1986, 60, 3315.
(28) Mahan, G. D.; Cole, H. S.; Liu, Y. S.; Philipp, H. R. Appl. Phys.
In the present paper, we have developed a set of Lett. 1988, 53, 2377.
relatively simple models, which permit to understand (29) Lazare, S.; Granier, V. Appl. Phys. Lett. 1988, 54, 862.
(30) Schildbach, K. Proc. SPIE 1990, 1279, 60.
basic features of laser ablation and even describe (31) Kleinschmidt, J.; Walther, J.U. Phys. Stat. Sol. (a) 1992, 131,
some experiments with sufficient accuracy. Despite 167.
Models for Laser Ablation of Polymers Chemical Reviews, 2003, Vol. 103, No. 2 551
(32) Furzikov, N. P. Appl. Phys. Lett. 1990, 56, 1638. (84) Valiev, K. A.; Velikov, L. V.; Dorofeev, Yu. I.; Skurat, V. E. Chem.
(33) Bäuerle, D.; Luk’yanchuk, B.; Schwab, P.; Wang, X. Z.; Arenholz, High Energy 1988, 22, 352.
E. In Laser Ablation of Electronic Materials  Basic Mechanisms (85) White, J. C.; Craighead, H. G.; Howard, R. E.; Jackel, L. D.;
and Applications; Elsevier: Amsterdam, 1992; p 39. Beringer, R. E.; Epworth, R. W.; Henderson, D.; Sweeney, J. E.
(34) Tokarev, V. N.; Lunney, J. G.; Marine, W.; Sentis, M. J. Appl. Appl. Phys. Lett. 1984, 44, 22.
Phys. 1995, 78, 1241. (86) Kudo, K.; Iwabuchi, T.; Muton, K.; Miyata, T.; Sano, R.; Tanaka,
(35) Luk’yanchuk, B.; Bityurin, N.; Himmelbauer, M.; Arnold, N. K. Jpn. J. Appl. Phys. 1990, 29, 2572.
Nucl. Instr. Methods B 1997, 122, 347. (87) Zienkiewicz, O. C. The Finite Element Method; McGrawHill:
(36) Arnold, N.; Luk’yanchuk, B.; Bityurin, N. Appl. Surf. Sci. 1998, New York, 1977.
127, 184. (88) Zwillinger, D. Handbook of Differential Equations; Academic
(37) Bityurin, N. Appl. Surf. Sci. 1999, 138139, 354. Press: Boston, 1989.
(38) Castex, M. C.; Bityurin, N.; Olivero, C.; Muraviov, S.; Bronni (89) Karlov, N. V.; Kirichenko, N. A.; Luk’yanchuk, B. S. Laser
kova, N.; Riedel, D. Appl. Surf. Sci. 2000, 168, 175. Thermochemistry; Cambridge International Science Press: 2000.
(39) Castex, M. C.; Bityurin, N. Appl. Surf. Sci. 2002, 197198, 805. (90) Arnold, N.; Luk’yanchuk, B.; Bityurin, N.; Bäuerle, D. Proc. SPIE
(40) Bityurin, N.; Castex, M. C. J. Appl. Phys. 2003, in press. 1998, 3343, 484.
(41) Bityurin, N.; Arnold, N.; Luk’yanchuk, B.; Bäuerle, D. Appl. Surf. (91) Wolfram, S. Mathematica, 4th ed; Wolfram Media/Cambridge
Sci. 1998, 127, 164. University Press, 1999.
(42) Arnold, N.; Bityurin, N. Appl. Phys. A 1999, 68, 615. (92) Luk’yanchuk, B.; Bityurin, N.; Anisimov, S.; Bäuerle, D. In
(43) Bityurin, N. Proc. SPIE. 2001, 4423, 197. Excimer Lasers; Laude, L. D., Ed.; Kluwer Academic Publish
(44) Bityurin, N.; Malyshev, A. J. Appl. Phys. 2002, 92, 605. ers: Dordrecht, 1994; p 59.
(45) Luk’yanchuk, B.; Bityurin, N.; Anisimov, S.; Bäuerle, D. Appl. (93) Brunco, D. P.; Thompson, M. Q.; Otis, C. E.; Goodwin, P. M. J.
Phys. A 1993, 57, 367. Appl. Phys. 1992, 72, 434.
(46) Luk’yanchuk, B.; Bityurin, N.; Anisimov, S.; Arnold, N.; Bäuerle, (94) Bartenev, G. M. Stability and Mechanisms of Polymer Destruc
D. Appl. Phys. A 1996, 62, 397. tion; Khimia, Moscow, 1984 (in Russian).
(47) Luk’yanchuk, B.; Bityurin, N.; Malyshev, A.; Anisimov, S.; (95) Guillet, J. Polymer Photophysics and Photochemistry; Cambridge
Arnold, N.; Bäuerle, D. Proc. SPIE 1998, 3343, 58. University Press: Cambridge, 1985.
(48) Lassithiotaki, M.; Athanassiou, A.; Anglos, D.; Georgiou, S.; (96) Srinivasan, R.; Hall, R. R.; Loehle, W. D.; Wilson, W. D.; Allbee,
Fotakis, C. Appl. Phys. A 1999, 69, 363. D. C. J. Appl. Phys. 1995, 78, 4881.
(49) Athanassiou, A.; Lassithiotaki, M.; Anglos, D.; Georgiou, S.; (97) Ball, Z.; Feurer, T.; Callahan, D. L. Sauerbrey, R. Appl. Phys. A
Fotakis, C. Appl. Surf. Sci. 2000, 154155, 89. 1996, 62, 203.
(50) Garrison, B. J.; Srinivasan, R. Appl. Phys. Lett. 1984, 44, 849. (98) Lazare, S.; Guan, W.; Drilhole, D. Appl. Surf. Sci. 1996, 9698,
(51) Garrison, B. J.; Srinivasan, R. J. Appl. Phys. 1985, 57, 2909. 605.
(52) Gorodetsky, G.; Kazyaka, T. G.; Melcher, R. L.; Srinivasan, R. (99) Taylor, R. S.; Singleton, D. L.; Paraskevopoulos, G. Appl. Phys.
Appl. Phys. Lett. 1985, 46, 828. Lett. 1987, 50, 1779.
(53) Kitai, M. S.; Popkov, V. L.; Semchishen, V. A. Makromol. Chem. (100) Samarskii, A. A.; Vabishchevich, P. N. Computational Heat
Macromol. Symp. 1990, 37, 257. Transfer; John Wiley: New York, 1995.
(54) Zweig, A. D.; Venugopalan, V.; Deutsch, T. F. J. Appl. Phys. (101) Himmelbauer, M.; Bityurin, N.; Luk’yanchuk, B.; Arnold, N.;
1993, 74, 4181. Bäuerle, D. Proc. SPIE 1997, 3093, 220.
(55) Hare, D. E.; Dlott, D. D. Appl. Phys. Lett. 1994, 64, 715. (102) Ortelli, E. E.; Geiger, F.; Lippert, T.; Wei, J.; Wokaun, A.
(56) Hare, D. E.; Franken, J.; Dlott, D. D. J. Appl. Phys. 1995, 77, Macromolecules 2000, 33, 5090.
5950. (103) Babu, S. V.; D’Couto, G. C.; Egitto, F. D. J. Appl. Phys. 1992,
(57) Bityurin, N.; Malyshev, A.; Luk’yanchuk, B.; Anisimov, S.; 72, 692.
Baeuerle, D. Proc. SPIE 1996, 2802, 103. (104) Himmelbauer, M.; Arenholz, E.; Bäuerle, D. Appl. Phys. A 1996,
(58) Luk’yanchuk, B.; Bityurin, N.; Anisimov, S.; Malyshev, A.; 63, 87.
Arnold, N.; Baeuerle, D. Appl. Surf. Sci. 1996, 106, 120.
(105) Paraskevopoulos, G.; Singleton, D. L.; Irwin, R. S.; Taylor, R. S.
(59) Zhigiley, L. V.; Kodali, P. B.; Garrison, B. J. J. Phys. Chem. B
J. Appl. Phys. 1991, 70, 1938.
1998, 102, 2845.
(106) Himmelbauer, M.; Arenholz, E.; Bäuerle, D.; Schichler, K. Appl.
(60) Albagli, D.; Dark, M.; Perelman, L. T.; von Rosenberg, C.; Itzkan,
Phys. A 1996, 63, 337.
I.; Feld, M. S. Opt. Lett. 1994, 19, 1684.
(107) Preuss, S.; Spaeth, M.; Zhang, Y.; Stuke, M. Appl. Phys. Lett.
(61) Anisimov, S. I.; Luk’yanchuk, B. S. PhysicsUspekhi 2002, 45,
1993, 62, 3049.
293.
(62) Braren, B.; Casey, K. G.; Kelly, R. Nucl. Instr. Methods B 1991, (108) Kautek, W.; Krueger, J.; Lenzner, M.; Sartania, S.; Spielman,
58, 463. Ch.; Krausz, F. Appl. Phys. Lett. 1996, 69, 3146.
(63) Kelly, R.; Braren, B. Appl. Phys. B 1991, 53, 160. (109) Stuart, B. C.; Feit, M. D.; Rubenchik, A. M.; Shore, B. W.; Perry,
(64) Afanasiev, Y. V.; Isakov, V. A.; Zavestovskaya, I. N.; Chichkov, M. D. Phys. Rev. Lett. 1995, 74, 2248.
B. N.; von Alvensleben, F.; Welling, H. Appl. Phys. A 1997, 64, (110) Oraevsky, A. A.; DaSilva, L. B.; Feit, M. D.; Glinsky, M. E.;
561. Mammini, B. M.; Paquette, K. L.; Perry, M. D.; Rubenchik, A.
(65) Kitai, M. S.; Semchishen, V. A. Quantum Electron. 1996, 26, M.; Small, W.; Stuart, B. C. Proc. SPIE 1995, 2391, 423.
517. (111) Stuart, B. C.; Feit, M. D.; Herman, S.; Rubenchik, A. M.; Shore,
(66) Hodapp, T. W.; Fleming, P. R. J. Appl. Phys. 1998, 84, 577. B. W.; Perry, M. D. JOSA B 1996, 13, 459.
(67) Luk’yanchuk, B.; Bityurin, N.; Anisimov, S.; Baeuerle, D. Appl. (112) Bityurin, N.; Malyshev, A. Appl. Surf. Sci. 1998, 127129, 199.
Phys. A 1993, 57, 449. (113) Malyshev, A. Yu.; Bityurin, N. M. Quantum Electron. 1999, 29,
(68) Bolle, M.; Lazare, S.; Leblank, M.; Wilmes, A. Appl. Phys. Lett. 134.
1992, 60, 674. (114) Frisoli, J. K.; Hefetz, Y.; Deutsch, T. F. Appl. Phys. B 1991, 52,
(69) Lazare, S.; Bolle, M.; Cros, A.; Bellard, L. Nucl. Instr. Methods 168.
B 1995, 105, 159. (115) Rosenfeld, A.; Ashkenasi, D.; Varel, H.; Wähmer, M.; Cambell,
(70) Hiraoka, H.; Gendova, M. Appl. Phys. Lett. 1994, 64, 563. E. E. B. Appl. Surf. Sci. 1998, 127129, 76.
(71) Dyer, P. E.; Farley, R. J.; Giedl, R.; Ragdale, C.; Reid, D. Appl. (116) Stoian, R.; Ashkenasi, D.; Rosenfeld, A.; Campbell, E. E. B. Phys.
Phys. Lett. 1994, 64, 3389. Rev. B 2000, 62, 13167.
(72) Dyer, P. E.; Karnakis, D. M.; Oldershaw, G. A. Appl. Surf. Sci. (117) Stoian, R.; Boyle, M.; Thoss, A.; Rosenfeld, A.; Ashkenasi, D.;
1995, 86, 1. Korn, G.; Hertel, I. V.; Campbell, E. E. B. In Technical Digest
(73) Mauser, H. Z. Naturforsch. 1967, 22B, 569. CLEO’2001, Baltimore, MD, Baltimore Convention Center, May
(74) Mauser, H. Z. Naturforsch. 1979, 34C, 1264. 611, 2001, p 577.
(75) Bityurin, N. M. Ph.D. Thesis, Inst. Appl. Phys., USSR Ac. Sci., (118) Srinivasan, V.; Smrtic, M. A.; Babu, S. V. J. Appl. Phys. 1986,
Gorkii, USSR, 1988. 59, 3861.
(76) Bityurin, N. M.; Genkin, V. N.; Sokolov, V. V. Sov. J. Polymer (119) Schmidt, H.; Ihlemann, J.; WolffRottke, B.; Luther, K.; Troe,
Sci. (Vysokomol. Soedin.) 1982, 24A, 748. J. J. Appl. Phys. 1998, 83, 5458.
(77) Bityurin, N.; Muraviov, S.; Alexandrov, A.; Malyshev, A. Appl. (120) Dyer, P. E.; Sidhu, J. J. Appl. Phys. 1985, 57, 1420.
Surf. Sci. 1997, 110, 270. (121) Kalontarov, L. I. Phylos. Magn. Lett. 1991, 63, 289.
(78) Bityurin, N.; Muraviov, S.; Alexandrov, A.; Bronnikova, N.; (122) Kalontarov, L. I.; Marupov, R. Chem. Phys. Lett. 1992, 196, 15.
Malyshev, A. Proc. SPIE 1997, 3093, 108. (123) Shlapintokh, V. Ya. Photochemical Conversion and Stabilization
(79) Dyer, P. E.; Oldershaw, G. A.; Schudel, D. J. of Phys. D  Appl. of Polymers; Hanser Publishers: New York, 1984.
Phys. 1993, 26, 323. (124) Blanchet, G. B.; Fincher, C. R., Jr. Appl. Phys. Lett. 1994, 65,
(80) Lapczyna, M.; Stuke, M. Appl. Phys. A 1998, 66, 473. 1311.
(81) Museur, L.; Zheng, W. Q.; Kanaev, A. V.; Castex, M. C. IEEE J. (125) Blanchet, G. B.; Shah, I. Appl. Phys. Lett. 1993, 62, 1026.
Sel. Top. Quantum Electron. 1995, 1, 900. (126) Dickinson, J. T.; JawJung, Shin; Jiang, W.; Norton, M. G. J.
(82) Riedel, D.; Castex, M. C. Appl. Phys. A 1999, 69, 375. Appl. Phys. 1993, 74, 4729.
(83) Tinone, M. C. K.; Tanaka, K.; Ueno, N. J. Vac. Sci. Technol. 1995, (127) Dickinson, J. T.; JawJung, Shin; Jiang, W.; Norton, M. G. Nucl.
13, 1885. Instr. Methods B 1994, 91, 672.
552 Chemical Reviews, 2003, Vol. 103, No. 2 Bityurin et al.
(128) Tsunekava, M.; Nishio, S.; Sato, H. Jpn. J. Appl. Phys. 1995, (137) Blanchet, G. B.; Cotts, P.; Fincher, C. R., Jr. J. Appl. Phys. 2000,
34, 218. 68, 2975.
(129) Blanchet, G. B.; Fincher, C. R., Jr. Appl. Phys. Lett. 1996, 68, (138) Mikheev, Yu. A.; Popravko, T. S.; Toptygin, D. Ya. Doklady AN
929. SSSR 1973, 210, 148.
(130) Blanchet, G. B. J. Appl. Phys. 1996, 80, 4082. (139) Gupta, A.; Liang, R.; Tsay, F. D.; Moacanin, J. Macromolecules
(131) Srinivasan, R.; Braren, B.; Casey, K. G. J. Appl. Phys. 1990, 1980, 13, 1696.
68, 1842. (140) Tonyali, K.; Jensen, L. C.; Dickinson, J. T. J. Vac. Sci. Technol.
(132) Hare, D. E.; Dlott, D. D. Appl. Phys. Lett. 1994, 64, 715. A 1988, 6, 941.
(133) Bennet, L. S.; Lippert, T.; Furutani, H.; Fukumura, H.; Masu (141) Bahners, T.; Schollmeyer, E. J. Appl. Phys. 1989, 66, 1884.
hara, H. Appl. Phys. A 1996, 63, 327. (142) Arenholz, E.; Wagner, M.; Heitz, J.; Bäuerle, D. Appl. Phys. A
(134) Odian, G. Principle of Polymerization, 2nd ed; Wiley: New York, 1992, 55, 119.
1970; p. 258. (143) Bityurin, N.; Arenholz, E.; Arnold, N.; Bäuerle, D., to be
(135) Zeldovich, Ya. B.; Raizer, Yu. P. Physics of Shock Waves and published.
HighTemperature Hydrodynamic Phenomena; New York, Aca (144) Aksenov, V. P.; Mikhailova, G. N.; Boneberg, J.; Leiderer, P.;
demic Press: 19661967, 2 vols. Muenzer, H. J. Proc. SPIE 2001, 4423, 70.
(136) Malyshev, A. Ph.D. Thesis, Inst. Appl. Phys. Russian Ac. Sci.,
N. Novgorod, 2002. CR010426B