IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. 31, NO.
12, DECEMBER 1995
A First-Order Model for Computation of
Laser-Induced Breakdown Thresholds in
Ocular and Aqueous Media: Part I-Theory
Paul K.
Abstract-An analytic, first-order model has been developed
to calculate irradiance thresholds for laser-induced breakdown
(LIB) in condensed media, including ocular and aqueuus media.
The model is derived from the simple rate equation formalism
of Shen for cascade breakdown in solids and from the the­
ory of multiphoton ionization in condensed media developed
by Keldysh. Analytic expressions have been obtained for the
irradiance thresholds corresponding to multiphoton breakdown,
to cascade breakdown, and to initiation of cascade breakdown by
multiphoton ionization of seed electrons (multiphoton initiation
threshold). The model has been incorporated into a computer
code and code results compared to experimentally measured
irradiance thresholds for breakdown of ocular and aqueous
media by nanosecond, picosecond, and femtosecond laser pulses
in the visible and near-infrared. The code and comparison of code
results to experiment have been documented in a second paper
(Part II).
I. INTRODUCTION
HE OPTICAL Radiation Division of Armstrong Labo­
T ratory is currently eugaged in a multiyear experimental
and theoretical research program to study how ultrashort laser
pulses interact with, propagate through, and damage ocular
tissue. One of the primary research goals is to gain an
experimental and theoretical understanding of laser-induced
breakdown (LIB) as a possible ocular damage mechanism. A
theoretical understanding of the damage caused by LIB in the
eye would be uscful in two fields: Laser safety, as a tool in
modeling ultrashort pulse ocular damage, and laser medicine,
where LIB is widely used as a cutting tool in ophthalmic laser
surgery [1], [2].
An understanding of the physics of ocular breakdown will
be gained through coupling experimental measurements to
theoretical models and numerical calculations. Among the
phenomena to be studied are: 1) the irradiance thresholds
corresponding to breakdown in ocular media and in fluids used
as simulants for ocular media, such as water and saline solution
[3]-[7], 2) the location, size, temperature, and time evolution
of the resulting plasma [1], l6J-llO], and 3) phenomena which
occur subsequent to plasma decay, such as cavitation bubble
Manuscript received March 24, 1995; revised July 28, 1995. This work was
supported byArmstrong Laboratory and by the Air Force Office of Scientific
Research (AFOSR) through Grant 2312AA-92ALOI4.
The author is with the Optical Radiation Division, Amlstrong Laboratory,
Brooks ArB, TX 78235 USA
IEEE Log Number 9415337.
0018-9197/95$04.00 © 1995 IEEE
2241
Kennedy
formation, bubble collapse, and propagation of shock and
acoustic waves [6], [7], [10]-[15]. Measurement and modeling
of LIB thresholds in ocular and aqueous media seems the
obvious starting point.
This paper documents the development of an analytic, first­
order model for computation of LIB thresholds in condensed
media, including ocular and aqueous media. The model is
based on the simple rate equation formalism of Shen [16] for
cascade breakdown in solids and on the model developed by
Keldysh [17] for multiphoton ionization in condensed media.
The model has been incorporated into a computer code and
code results have been compared to experimentally measured
irradiance thresholds for breakdown of ocular and aqueous me­
dia by nanosecond, picosecond, and femtosecond laser pulses
in the visible and near-infrared. The code and comparison of
code results to experiment have been documented in a second
paper.
In the next section, the two mechanisms for LIB are
discussed and a description is given of the general approach
used here in modeling LIB in condensed media. Sections III
and IV deal with the modification of Shen's rate equation
formalism to include multiphoton ionization effects and with
the solution to the modified rate equation, respectively. In
Section V analytic expressions are obtained for the irradiance
thresholds corresponding to cascade breakdown, multiphoton
breakdown, and multiphoton initiation of cascade breakdown.
A summary is given in Section VI.
II. OPTICAL BREAKDOWN IN CONDENSED MEDIA
Dielectric breakdown through optical absorption of laser ra­
diation, also called optical breakdown or laser-induced break­
down, is the partial or complete ionization of a solid, liquid,
or gas through absorption of laser energy [16]. The ionization
results in a "gas" of charged particles, a plasma, which absorbs
optical radiation much more strongly than ordinary matter. The
plasma can thus be rapidly heated by the laser beam to very
high temperatures, producing plasma expansion, an audible
acoustic signature, and a visible plasma emission.
Some plasmas produced by partial ionization may not be
dense enough to significantly interllct with II laser beam_ Tbese
cool, diffuse plasmas do not correspond to breakdown. The
term optical breakdown, as used in this paper, will be limited
to either complete (single) ionization of a diffuse medium such
as a gas or to partial ionization of a condensed medium which
2242 IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. 31, NO. 12, DECEMBER 1995

produces a plasma dense enough to significantly absorb laser For cascade breakdown at least, experimental measurements
light. The latter is typically defined to be approximately 1018 in water show a field dependence similar to that found in
electrons/cm3 [3], [18]. solids [3], [31]. To obtain a simple, first-order model for
There are two mechanisms which can lead to LIB: Direct liquid breakdown, we will assume that liquids can be treated
ionization of the medium by multiphoton absorption [16], [17], as amorphous solids with (effective) conduction and valence
[19]-[22] or cascade ionization, also called avalanche ioniza­ bands. This appears to be a reasonable approximation for
tion [15], [16], [18], [21]-[26]. The latter process requires pure liquid water and for water doped with halide salts [29],
one or more free electrons to be present in the focal volume [30]. The models of Shen [16], for cascade breakdown in
at the beginning of the pulse. These "seed" electrons absorb solids, and Keldysh [17], for multiphoton ionization in crystals,
light photons through collision witli atoms or molecules, a have tlierefore been adapted to model breakdown in aqueous
process known as inverse brcmsstrahlung absorption. Having media. Altliough the model was developed for application to
achieved an energy greater than the ionization potential, a free aqueous solutions, it can be applied to breakdown in any
electron may ionize a molecule by collision. This produces two condensed medium which can he treated as a semiconductor
free electrons of lower energy, which in tum absorb energy or amorphous semiconductor.
from the laser and ionize two more, tlie process continuing
geometrically in an electron "cascade" leading to breakdown. m. MODIFIED RATE EQUATION FOR
In an impure medium seed electrons are most likely to come CONDENSED MATTER BREAKDOWN
from easily ionized impurities which act as shallow donors.
For nanosecond and sub-nanosecond pulses, we will have
The ionization may occur through tliennally induced collisions
three breakdown regimes. 1) A long pulse regime dominated
or by optical absorption of one or more photons. In a pure
by cascade ionization where multiphoton ionization plays no
mcdium with a high ionization potential, ionization of a few
significant role except (perhaps) for providing seed electrons.
molecules in the medium by multiphoton absorption may be
2) A short pulse regime where both types of ionization are
required to produce seed electrons and start a cascade.
significant. In this regime the pulse may be so short that a
Multiphoton ionization is a nonlinear optical process which
cascade cannot build up during the pulse unless the initial
typically becomes significant only at high irradiances and for
carrier density is very high. This high initial density would
wavelengtlis in tlie near-IR or shorter. For "pure" multiphoton
have to be provided by multiphoton ionization; i.e., multipho­
breakdown each electron is independently ionized, requiring
ton processes would ')ump start" the cascade. For irradiances
no seed electrons and no collisions or particle-particle interac­
high enough to achieve tliis, continuing multiphoton ionization
tions. The breakdown process is thus independent of impurities
might contribute to and accelerate the cascade process. 3)
and can occur even in media too diffuse to allow many
An ultrashort pulse regime, where only "pure" multiphoton
collisions during the pulse duration. It is potentially much
ionization is fast enough to allow breakdown to occur. over
faster than the buildup of an electron cascade and can tlierefore
the timewidtli of tlie pulse.
occur even for the shortest laser pulses.
In modeling condensed matter breakdown by ultrashort
Both multiphoton and cascade breakdown can occur in
pulses, it is clearly desirable to have a formalism which
solids, liquids, or gases. For cascade breakdown inside con­
includes both cascade and multiphoton effects. In this section,
densed media, however, the term "free electron" takes on a
tlie rate equation formalism of Shen [16], which modcls cas­
somewhat different meaning tlian witli gases. In condensed
cade breakdown only, will be modified to include multiphoton
media we have both electrons which are bound to a particular
ionization. A solution to this modified rate equation will be
molecule or lattice site and electrons which are free or quasi­
sought in Section IV.
free; i.e., tlieir kinetic energy is great enough that they can
Shen divides the breakdown process into two parts: seed
move through the liquid or solid lattice without being trapped
electron generation and cascade ionization. An initial free
by localized potential wells. As long as these quasi-free
carrier density Po is assumed, which may come from multi­
electrons have sufficient mobility to undergo collisions and
photon ionization or ionization due to thermalizing collisions.
absorb photons, an electron cascade can occur. In modeling
Breakdown is assumed to occur when the free electron density
condensed matter breakdown, transitions between bound and
p reaches a critical value Per"'" 10 1 8 /cm3 . The rate equation
quasi-free states are the equivalent of molecular ionization in
is solved to obtain HIe free carrier density as a function of
gases.
time, pet). This solution is combined witli the breakdown
Numerous researchers have modeled cascade and multi­
criteria and witli a classical model for free carrier absorption of
photon ionization in gases [16], [17], [19]-[24] and solids
optical field energy. The result is an equation for the threshold
[16]-[18], [25]-[28], with results that give a reasonable match
irradiance needed to raise the carrier density from Po to Per
to experimental data. Breakdown in liquids, sllch as water
by cascade ionization during a pulse of duration Tp. A more
and aqueous solutions, has been experimentally investigated
general form of the rate equation will now be derived which
[3]-[15]; but is less well understood tlieoretically than solid
includes multiphoton contributions to carrier buildup during
or gas breakdown. The amorphous nature of tlie medium, the
the cascade phase as well as during seed electron generation.
consequent vmiation in the localized potential seen by the
Variation in electron density as a function of time can be
quasi-free electron, and the fact that molecules in liquid water
expressed in tlie generalized form [16], [18]
tend to associate or cluster in an undetermined fashion [29],
[30], all make electron mobility in water highly complex [3]. 8p/at = (17 - g)p + (8p/at)m, (1)
KENNEDY: A FIRST-ORDER MODEL FOR COMPUTATION OF LASER-INDUCED BREAKDOWN THRESHOLDS: PART I-THEORY
which is simply the Shen equation plus a multiphoton term.
The first term on the right-hand side represents cascade mul­
tiplication, where the cascade ionization rate, "7, is the proba­
bility per unit time that a free electron will have an ionizing
collision with a bound electron. The second term represents
free electron losses due to recombination, trapping, and diffu­
sion out of the focal volume of the beam. The electron loss
rate, g, combines the effects of all these processes. The final
term represents carrier generation by multiphoton ionization
during the cascade process.
In order to place (1) in a form which can be solved, we
assume
where Pb(t) is the density of bound electrons with binding
energy Eion at time t and r/ is the multiphoton ionization rate
for states of binding energy Eion. We can also write
Pb(i) =npmol - pet) ,
where n is the number of electrons/molecule with binding
energy Eion and Pmo] is the molecular density. The first term
in (3) is the maximum density of bound electrons, which is
reduced by the density of free carriers pet). For condensed
media P mol � 1022 - 1023/cm3. The free carrier density, on
the other hand, will probably not go higher than p � 10 2o /cm3
even at breakdown [9]. Neglecting the last term in (3), the
bound electron density may be considered as approximately
constant in time, giving
"7' Pb
(ap/at)m � � r/ npmol·
The modified rate equation now takes the soluble form
op/at - (71 - g)p = "7'Pb·
IV. SOLUTION TO THE MODIFIED RATE EQUATION
A. Free Carrier Density
Equation (5) can be solved to obtain the free carrier density
p( t) by placing it in the form
op/at - ap= b,
a=71 - 9 = constant,
b = r/Pb = constant.
Equation (6) has an integrating factor of the form
exp (/ -adt) =exp(-at)
and a solution of the form [32]
pet) =exp (at) [it b exp (-at) dt+ ] c
, ( 7)
where c is a constant of integration. Equation (7) gives
pe t) (-b/a)[l - cxp(at)] + c exp (at)
= In MKS units, the peak irradiance Io(W/m2) is related to the
p(O) c= Pu
=
pet) =Po exp(at) + (b/a) [exp(al) - 1].
2243
Differentiating,
op/ot=apo exp(at)+b exp(ai), (9)
and substituting, (8) is shown to be a solution of (6).
Numerical calculation of the free carrier density using (8)
requires experimental measurements or theoretical estimates of
"7, g, "7', and Po· Analytic expressions for these quantities will
now be derived beginning with the cascade ionization rate.
B. Cascade Ionization Rate
Following Shen, the cascade ionization rate is obtained from
a classical model of free electron-electric field interaction.
(2) A free electron of mass m and charge e interacts with an
alternating electric field of frequency w and rms field strength
E. The electron absorbs energy from the field only during
collisions with atoms or molecules (inverse bremsstrahlung
absorption). The electron gains energy at a rate given by [21]
(3) dE/dt=(e2E2/mw2)u[w2/(w2+ u2)], (10)
where
(11)
is the effective collision frequency, na the atomic (or molec­
ular) density, Ve the electron velocity, and O"tr the electron
transport cross section. Equation (10) is the average rate of
gain for one of an ensemble of electrons.
An energetic electron that collided with a heavy particle and
did not absorb a photon could lose energy rather than gaining
it. Energy losses from elastic collisions are given by [21]
(4)
dE/dt = -2(m/M)EavV[W2/(w2+ v2)], (12)
(5)
where Eav is the average electron energy and M is the atomic
(or molecular) mass. Combining (10) and (12), the energy of
the average electron changes at a rate
dE/dt = [(e2E2/m) - (2mEavW2/M)]v / (w2 + v2). (l3)
The mean free time between collisions is
T = l/v, (14)
also called the momentum transfer collision time. Multiplying
(6)
the numerator and denominator of (13) by T2,
(6a)
(6b) dE/dt= [(e2E2/m) - (2mEavw2/M)]T/(w2r2 + 1). (15)
The first term of (15) is the expression given by Shen for rate
of electron energy gain. (Shen omits colli�ional losses).
We now assume that any electron whose kinetic energy
reaches the ionization energy, Eion, will shortly produce
a new free electron. Statistically, there will be individual
electrons that violate this assumption, but it is a reasonable
approximation. Dividing (15) by Eion thus gives the cascade
ionization rate
"7 = [(e2E2/m) - (2mEavw2/M)]T/(w2T2 + l)Eion. (16)
rms field E(V/m) by [33]
(8) (17)
2244 IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. 31, NO. 12, DECEMBER 1995

where Co is the permittivity of free space, c is the vacuum D. Multiplwton Ionization Rate
speed of light, and no is the index of refraction of the medium L V. Keldysh [17] has derived approximate expressions
at frequency w. Equation (16) now becomes for the probability of mulliphoton' ionization, both in gases
and in condensed media. Ionization in the latter case refers to
71 = [(e2 lo/menoco) - (2mcavW2/M)]T/(w2T2 + l)Eion.
an electron transition from the valence, band to a conduction
(18)
or exciton band, creating an electron-hole p�ir. The condensed
media expression should be applicable to multiphoton ioniza­
C. Electron Loss Rate
tion in water and aqueous solutions, which can be treated as
The electron loss rate, g, consists of contributions from amorphous scmiconductors [29].
recombination, trapping, and diffusion [22J. We will assume In modeling ionization by a strong electromagnetic wave, a
that the lifetime of the quasi-free electron is longer than the key parameter is the ratio, ry, of the opticaJ frequency wand
interaction time for pulsewidths of interest (Tp S 10-8 sec), the tunneling frequency Wt:
especially when the electron is absorbing energy from an
intense optical field. Electron-hole recombination during the
,=w/wt=w(m'6.)1/2/eE. (25)
breakdown process will therefore be neglected. In (25) m' represents the exciton reduced mass
Trapping in localized potential wells or solvated states is a
well known phenomenon in liquid water [34J-[36J. Binding lim'= l/m + l/mh, (26)
energies of these states, however, are low enough (�1.5 ±
where m and mh are the electron and hole masscs, respec­
0.5 eV) that they can be easily reionized by cascading free
tively, and 6. is the transition energy across the band gap,
electrons or by single photon absorption. We will assume for
equivalcnt to the ionization energy Eion in our notation.
our first-order model that solvation and desolvation do not
Keldysh first derived a general formula, valid for any value
significantly effect the breakdown process at fields close to
of ,. He then obtained approximate fonllulas for the low
the breakdown threshold.
frequency (, � 1) and high frequency (ry � 1) limits,
With the above assumptions the loss rate is the rate of
cOITesponding to tunneling ionization and ionization through
diffusion out of the focal volume, given by [22J, [23]
multiphoton absorption, respectively.
For multiphoton ionization it is useful to define an effective
(19)
ionization potential in the field E:
where Td is the average time the electron stays in the focal
volume, D is the electron diffusion coefficient, and A is the
6.' = 6. + e2 E2 /4m' wZ = 6.[1 + 1/4ry21. (27)
characteristic diffusion length. The diffusion coefficient is [23], The number of photons required to ionize is then
[24]
K = (1 + 6.' /fiw), (28)
D = 2cav/3mv, (20)
where the symbol (x) denotes the integer prui of the number
where Cav is once again the average electron energy. For x, Ft = h/27r, and h is Planck's constant. Using (25), (27), and
a cylindrical focal volume of diameter d and length e, the (28), Keldysh's expression for the probability of mllltiphoton
diffusion length is given by [22] ionization in condensed media takes the form

(21) W= (2/97r)w(m'w/fi)3/2 exp[2K(1 - 1/4ry2)]

We assume a gaussian beam and define the focal volume
<I>(z)(1/16ryZ)K, (29)
to be the region extending for one-half the Rayleigh range, where
ZR, on either side of the beam waist. Since the beam diameter
v arie s little over this region, the volume is approximately a z = [2K - 26.'/fiwP/2, (30)
cylinder of dimensions
and the function <I>(z) represents Dawson's Integral [37]:
d = 2ro,

1:=ZR = 7r(ro)2/A = 7rd2/4A,

(22)
(23)
<p(z) = exp (_z2) lZ exp (yZ) dy = exp (_zZ)

where A is the optical wavelength and To is the gaussian waist 2....= [z2nH /n!(2n + 1)]. (31)
n=O;oc>
radius. The focal volume is given by
Equation (29) has a rather complex dependence on the
(24)
optical field E, which can be greatly simplified by using the
Smaller focal volumes and spot sizes will produce a higher limiting condition, ry � 1, to obtain:
rate of diffusion loss and should cause a higher breakdown
1 ± 1/4ry2 ;:;::;1, (32)
threshold for pulses longer than the diffusion time (Tp � Td)'
6.' ;:;::; 6., (33)
According to Bloembergen [18], for pulses of 10-8 sec or
less we will usually have Td ::; Tp in condensed media, making K;:;::; (1 + 6./,hw) , (34)
diffusion losses during the pulse interaction time small. z ;:;::; [2K .26./nw]1/2. (35)
KENNEDY: A FIRST-ORDER MODEL FOR COMPUTATION OF LASER-INDUCED BREAKDOWN THRESHOLDS: PART I-THEORY 2245

With these changes the field dependence is confined to the last and (37), we obtain the free electron density generated in time
term. Using (25) and (17), we can convert to a dependence on !:J.t by interaction with a pulse of irradiance 10:
irradiance:
(46 )
(36)
Assuming the initial density is that generated on the leading
Finally, using (32)-(36) in (29), the dependence of mul­ edge of the pulse, we follow Sacchi [3] and somewhat arbitrar­
tiphoton ionization on optical irradiance takes the familiar ily set 6t = Tp/IO. We further assume that if Tp represents the
form full width half maximum (FWHM) in irradiance of the pulse,
then on the leading edge the irradiance will be roughly half
W =A[Blo]K, (37) the peak irradiance 10, We now have
A = (2/97r)w(rn'w/tt)3/2 exp [2K]<T>(z)(1/16)K, (38)
(47)
B = [e2/rn'6w 2cEono]. (39)
The initial density generated by thermal excitation can be
All quantities above are in MKS units. B has units of inverse estimated by assuming that the molecules are a thermalized
irradiance [rn2/Wj and A has units of inverse time and volume Maxwell-Boltzmann distribution with temperature T. The
[sec-1 m-3]. bound electrons correspond to thc ground state of the distribu­
The probability W gives thc number of ionizations (or free tion and the ionized electrons to the excited state, where Eion
carriers gencratcd) per unit volume per unit time. It is thus is the transition energy between states. Maxwell-Boltzmann
equivalent to the time rate of change of the free carrier density statistics give a probability
P due to multiphoton ionization, which is also given by (4)
and (6b): (48)

that a particular particle will be in an excited state due

W = (8p/8t)m = r/Pb = b. (40)
to thermal excitation, where kB is the Boltzmann constant.
We can now compute the multiphoton ionization rate Considering P as the ionization probability and multiplying
by the density of bound electrons with binding energy Eion,
(41) we have

as a function of the input il!adiance 10, just as we did for the (49)
cascade ionization rate 7].
If the field interacts with the medium for a time 6t, then If there are multiple sources for seed electrons (medium,

the fraction of bound electrons ionized in the focal volume is impurities, traps), then (47)-(49) must be solved for each
source, with the appropriate binding energy and bound electron
a = 7]'6t = P/Pb' (42) density in each case. Each term in (45) would then represent
the sum of contributions from all carrier sources present. Note
The free electron density generated by multiphoton ionization
that seed electrons contributed by impurities can significantly
is
lower the breakdown threshold for some impure media at some

P= apb W6t, (43) pulsewidths and wavelengths.

=

and the number of free electrons in the focal volume is V. BREAKDOWN THRESHOLDS

(44) From (8) and the expressions derived previously for 7], g,
a, r/, b, and Po, we can predict the electron density p( t)
E. Initial Free Carrier Density
at some time t during the passage of a pulse of width Tp,

frequency w, and peak irradiance 10, More commonly, we wish

The initial free carrier density, Po, may come from ion­
to determine the threshold irradiance required to produce the
ization of molecules in the medium, ionization of impurities,
critical electron density, Per, that corresponds to breakdown.
or ionization of carriers in localized shallow traps. The two
Unfortunately, no analytic expression for breakdown threshold
ionizing mechanisms are optical absorption of one or more
is derivable from the general formalism of (8). The inclusion
photons and thermal excitation. In condensed media the latter
of both cascade and multiphoton effects creates an extremely
could refer either to molecule-molecule collisions in liquids
complex dependence of pet) on irradiance, although a thresh­
or to molecular interaction with lattice vibrations (phonons)
old could be numerically determined from a calculation and
in solids or in liquids with some extended order [3]. We now
plot of pet) versus 10,
define
An analytic expression for breakdown threshold can be
derived when only one ionization mechanism contributes to
Po = Pot + Pam, (45)
the carrier buildup from po to Per. If multiphoton contributions
where Pot and Pom represent densities generated by thermal to the carrier buildup are neglected, then (8) can be used to
excitation and multiphoton ionization, respectively. compute an irradiance threshold for cascade breakdown. Using
The initial density generated by multiphoton ionization can the Keldysh formalism given in Section IV -D, analytic expres­
be estimated from the model given previously. Combining (43) sions can also be obtained which give the irradiance thresholds
2246 IEEE JOURNAL OF QUANTUM ELECTRONICS. VOL. 31. NO. 12. DECEMBER 1995

for pure multiphoton breakdown and for initiation of cascade
breakdown by multiphoton ionization of seed electrons. Before
deriving these expressions, a clearer definition of breakdown
criteria is needed for future use in comparing the results of
the model to experiment.
arbitrary and alternate values could be used. The values above,
however, seem to work well in the comparison of theory to
experimental data.
A problem arises in attempting to use the standard endpoint
to detect breakdown by pulses shorter than 10 ps; i.e., the
intensity of the plasma radiation decreases as the pulsewidth

A. Definition of Breakdown becomes shorter. Eventually it becomes undetectable by the

naked eye, which is the standard detector for visible plasmas
The standard definition of breakdown is a critical free
produced by long pulse breakdown. A visible plasma, how­
carrier density Per ::::::.1018 /cm3 [3], [18]. This represents ap­
ever, is not the only breakdown-induced phenomenon used'
proximately the minimum density at which significant optical
in the literature as an experimental endpoint. Zysset et at.,
absorption begins to occur in the plasma. When performing
[6J used detection of a cavitation bubble, produced as an
theoretical calculations for comparison to most experimental
,

aftereffect of plasma formation, as an endpoint in studies of

data, this estimate is probably inappropriate. The standard
water and saline breakdown by 40 picosecond Cps) Nd: YAG
experimental endpoint for LIB measurements is a plasma
laser pulses. A "bubble" endpoint similar to this has been
hot enough and dense enough to produce a visible emission
used by Armstrong Lab iIi measuring LIB thresholds for 100
[3]-[7]. Such visible plasmas, referred to hereafter as the
femtosecond (fs) pulses at 580 nm. We did not attempt to
"flash" endpoint, almost certainly represent densities higher
detect the expansion and collapse of the initial cavitation
than 1018/cm3.
bubble, which occurs on microsecond time scales [11]. Instead
An estimate of visible plasma densities can be obtained from
we looked for the smaller and longer lasting bubbles produced
the work of Barnes and Rieckoff [9], who measured plasma
in the focal region by diffusion of gas into the, oscillating
emission from water breakdown produced by 30 nanosecond
cavitation bubble [39].
(ns) ruby laser pulses. Spectral measurements were used
Bubble formation was observed at threshold e�ergies of
to calculate plasma temperature using Planck's equation for
only a few microjoules CjiJ) per p�lse. On the other hand,
blackbody emission. The calculated temperature of 15 000 K
pulse energies two orders of magnitude higher (100-200 I'lJ),
was then used in a model developed for solar plasmas to give
which represent the highest energies available with our current
a fractional ionization of ex :::::: 3 X 10-3.
system, were insufficient to produce flashes visible to the
The molecular density of liquid water is
naked eye. The bubble endpoint clearly represents plasmas
3
= (1 gm/em ) x (1 mole/IS gm) which are smaller, cooler, and less dense than those associated
P mo l
with visible emission. Theoretical thresholds corresponding
x (6.02 X 1023 molec./mole)

22 molec.lcm3• to the bubble endpoint will therefore be calculated using

= 3.34 x 10 (50 )
llt = Tp as the breakdown time and Per = 1018/Cm3 as
the estimated critical density. The analytic expressions derived
The minimum "ionization energy" in liquid water is 6.5 eV
for breakdown thresholds in the remainder of Section V
[3], [29], [30], [35J, representing a transition from the Ib1
will assume the standard (flash) endpoint unless otherwise
molecular orbital to an exciton band [29]. There are a pair of
specified. The expressions can be modified for the bubble
such bound electrons for each water molecule (n = 2), giving
endpoint by substituting the breakdown time and critical
Pb = npmol -,:: 6.68 x 1022 bound electrons/cm3, (51 ) density given above.

as the density of bound electrons with this ionization energy.

B. Irradiance Threshold for Cascade Breakdown
With a fractional ionization of 0.3% the critical density at
'
breakdown is We now turn to the derivation of an irradiance threshold
fth, for cascade breakdown. This is defined to be lhe minimu�
Per = exPb = 2 X 1020 free electrons/cms. (52) �adi�ce which satisfies the breakdown criteria just specified;
l.e., raIses the carrier density from Po to Per = 1020/cm3
For future calculations of thresholds corresponding to the flash
during 0.5 Tp. Following Shen, we assume that there is a
endpoint, Pcr 1020/ cm3 will be used as the breakdown
critical cascade ionization rate,17cr, that corresponds to setting
=

criterion.
The flash endpoint also introduces a constraint on the time
fo = fth in (18); and further that this is the value of 17 for
whi h (8) yieJds the breakdown condition P (0.5 Tp) = Per.
allowed for breakdown. During the timewidth of the pulse, �
Settmg b = 0, to eliminate multiphoton contributions, and
Tp, both plasma formation (breakdown) and plasma heating to using (6a) gives
visibly eniitting temperatures must occur. Reichel et al., [38],
found that breakdown occurred during the first half of a 20 ns
Nd : YAG laser pulse, with the remaining pulse energy going
p(t) :::::: Po exp [(17 - g)t]. (53)
to plasma heating. Future calculations for the flash endpoint
will use Tp/2 as an estimated breakdown time, regardless of Now we apply the breakdown criteria to obtain

whether cascade or multiphoton ionization is the dominant

mechanism. It should be noted that these choices of breakdown Per = Po exp [(17er - g)O.5Tp], (54)
time and critical density for the flash endpoint are somewhat 1]er = g + 2(Tp)-1 In (Per/Po)' (55)
KENNEDY: A FIRST-ORDER MODEL FOR COMPUTATION OF LASER-INDUCED BREAKDOWN THRESHOLDS: PART I-THEORY 2247

Setting (5�) equal to the expression for 'fIer obtained by setting initial density Po � po(min). The second, the multiphoton
fa = fth m (18), the threshold is initiation threshold Im, represents tlJe irradiance needed to
nit ate a cascade by providing
� � Po (min) through multiphoton
Ith = [mcnocoEion(1 + W2 'T2 )/c2'T][g + 2(7p)-1 In (Per/Po)] .
101llzatlOn.
+ 2m2EavW2 (cnoE:o)/e21Vf, (56) Equation (47 ) gave the initial density Pam generated through
multiphoton ionization by the leading edge (Llt = 0.1 'T ) of
,:here all quantities are in MKS units [Ith in W/m2]. A
SImpler form can be obtained if we assume that the average
a pulse witlJ peak irradiance Io. To compute tlJe thre hold :
electron energy is
10 = Im, we set Pam = po(min) and obtain

(57) (61)

for an ensemble of quasi-free electrons whose kinetic energies

lie between 0 and Eion. Equation (56) can now be written as the necessary peak irradiance, where 1m/2 is the value
on the leading edge tlJat actually generates po(min). From
Ith = [CI(l + W2 'T2 )/'T][g + 2('Tp)-1 In (Per/ Po)] (58) it is clear that tlJe minimum initial density Po (min)
+ CI mw2/M, (58) corresponds to the maximum irradiance needed to sustain
cascade breakdown:
where

(59) (62)

The three terms of (58) represent, in order, diffusion losses, D. Time Constraints for Cascade Breakdown
carrier buildup through cascade ionization, and collisional
In addition to the minimum initial density constraint given
energy losses.
above, there is also a time constraint on the initial density
The dependence of the cascade breakdown threshold on
needed for cascade breakdown during a time 0.5 'Tp. Bloember­
various experimental parameters can be seen from (58) and
gen [18] estimates that the time between collisions, for a quasi­
(59). The threshold is directly proportional to tlJe ionization
free electron in a condensed medium, is approximately 'T �
energy Eion. For optical frequencies and photon energies high
lO-lu s. Since collision and photon absorption is occurring
enough to give W2'T2 � 1, fth is proportional to w2 (or to 1/.\2
on a femtosecond time scale, a cascade could conceivably
as it is more commonly expressed). When tlJe loss terms are
small, as they are likely to be for short pUlses, the threshold is
raise p( t) by a factor of 1012 in a picosecond or less [28].
For subpicosecond pulses, however, it may not be possible to
inversely proportional to the pulsewidth 'Tp. Finally, for pulses
long enough to make diffusion a factor ('Tp > 'Td), smaller spot
achieve cascade multiplication from po(min) to Per over an
interaction time 0.5 'Tp. In this case a higher minimum initial
sizes will produce higher thresholds, due to a higher rate of
density, p�(min), must be defined; for which breakdown can
diffusion loss from the smaller focal volume.
be achieved over this time.
We begin by obtaining an estimate of the minimum time
C. Irradiance Threshold for Multiphoton Initiation
needed to go from po(min) to per by cascade ionization. The
Although (58) neglects multiphoton contributions during multiplication factor during this event is
carrier buildup, multiphoton ionization may still contribute to
the generation of the initial free carrier density po. To initiate
(63)
cascade ionization tlJere must be at least one seed electron in
the focal volume, Vj. In fact, only one seed electron makes
where y represents the number of times the density doubles
cascade initiation uncertain and 10 seed electrons would be a
during the cascade. The time required for one free electron to
more dependabJe starting point, especially for ps and fs pulses,
ionize another is approximately
where the short pulse duration requires rapid initiation. We
assume a minimum value of tlJe initial free electron density
(64)
(60)
where Neall is tlJe number of collisions needed to absorb one
where No(min) represents the minimum number of seed
photon and K is the number of photons needed to ionize. The
electrons required in Vj. In our calculations No(min) was
ionization time is also tlJe minimum doubling time 'Tdb; i.e., the
set to 1 for ns pulses and to 10 for ps and fs pulses.
time during which the number of free electrons N in the focal
For some condensed media, such as semiconductors, ther­
volume will double, assuming tlJere are no losses. With these
mal ionization at room temperature will supply sufficient free
definitions, the minimum breakdown time can be estimated as
carriers, 108 /cm3 to satisfy tlJis condition [18]. For pure
Pot � ,

water, however, free carrier density is negligible [291 and seed

electrons must be supplied by multiphoton ionization. In the 'TBR = 'Tdb(Y + 1), (65)
latter case there will actually be two thresholds associated with
cascade breakdown. One, Ith as given by (58), represents the where the symbol ( ) once again denotes the integer portion
irradiance needed to sustain a cascade to breakdown, given an of the number enclosed.
2248 IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. 31. NO. 12. DECEMBER 1995

If O.5'Tp 2' 'FIR., then full cascade breakdown from p o { min ) be obtained from (46) with !It = 0.5 'p' 10 = IMP; and
is possible and no recalculation of the thresholds in Section P =
Per:
V -C is needed. Otherwise, we compute
(74)
y' O.5'Tp/'db,
= (66)
' . ) Since multiphoton absorption is a nonlinear optical process
' = 2Y = Pcr/ Po/ ( mIn, (67)
.1:
requiring very high irradiance, IMP is likely to be higher than
p� ( mi n) = Pcr/X', (68)
cascade breakdown thresholds in almost all cases. Tn the fem­

where y' is the largest number of doublings possible in the tosecond pulse regime, however, time constraints on cascade

time allowed, x' is the corresponding multiplication factor, and formation cause a gradual shift to rnultiphoton ionization as

p� ( min) is the new minimum initial density. From (47), we can the dominant mechanism.

define a new multiphoton initiation threshold, that generates

this new initial density: VI. SUMMARY

(69) A first-order model has been developed to calculate irra-

diance thresholds for laser-induced breakdown in condensed
Since p� ( min ) > po(min), we have 1;" > 1m. On the other media, including ocular and aqueous media. The model is
hand, the irradiance needed to sustain the cascade, primarily an extension of Shen's simple rate equation for­
malism for cascade breakdown in solids. Multiphoton effects
(70)
have been coupled into this formalism using the theory of
decreases from the maximum value of albeit slowly since . multiphoton ionization in condensed media developed by
(62),
the dependence on Po is logarithmic. The pair of thresholds Keldysh. The model has two parts.
[1;",I�h] replace [1m,IU1(rnaxl] for pulses short enough that First, a general expression has been derived which gives
'TJ3R> 0 .5 'p. free electron density as a function of input irradiance, when
both multiphoton and thermal seed carrier generation are
E. Measured versus Theoretical Cascade Thresholds present and when plasma buildup has .contributions from both
cascade and multiphoton ionization. No analytic expression
Having obtained theoretical expressions for the cascade
for breakdown threshold can be derived in this general case,
breakdown and multipholon initiation thresholds, we now
although a threshold could be numerically detennined from a
consider which of these corresponds to the measured threshold.
calculation and plot of density versus irradiance.
In this discussion only 1m and 1th(max) will be mentioned;
Second, analytic expressions have been derived for break­
but r:n and I�h are implied for the time regimes where they
down thresholds when only one ionization mechanism con­
are applicable.
tributes to carrier buildUp. The irradiance thresholds for mul­
There are two cases to consider. If 1m > Ith(max), then 1m
tiphoton breakdown, cascade breakdown, and multiphoton
will be the experimentally measured value for cascade break­
initiation of cascade breakdown, can be easily calculated from
down. For Ith(max) > 1m, on the other hand, the measured
the model.
threshold should be some interinediate value. This value can
The model has been incorporated into a computer code and
be found by incrementally increasing the initial density starting
code results compared to experimentally measured irradiance
from Po = po(min ) . As Po is increased the multiphoton
thresholds for breakdown of ocular and aqueous media by
initiation threshold will go up and the cascade breakdown
nanosecond, picosecond, and femtosecond laser pulses in the
threshold will go down, until at some value, Po = p�, they
visible and near-infrared. The code and comparison of code
become equal:
results to experiment have been documented in a second paper
1� = [p�/A(0.hp)]1/K,
2B-1 (71) (Part II).
I�� Ith [Po = p�],
= (72)
I�� = 1�. ACKNOWLEDGMENf
(73)
The author would like to thank Dr. M. Rogers, Dr. P.
The discussion above, of course, applies only to media where
Roach, and Dr. R. Thompson for valuable discussions on
thermal processes do not generate sufficient seed electrons
laser-induced breakdown.
and multiphoton initiation is needed. For media where Pot 2'
po ( rnin ) for 0.5 'p 2' 'DR, or Pot 2' p�( = min) for pulses of
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Paul K. Kennedy received the B.S., M.S., and
Ph.D. degrees in physics from North Texas State
University in 1976, 1980, and 1983, respectively.
In 1983, he joined the Rocketdyne Division of
Rockwell International, where he served as a the­
oretical analyst and scientific programmer support­
ing research and development of high energy free­
electron, excimer, and oxygen-iodine lasers. Since
1992, he has been a research biophysicist in the Op­
tical Radiation Division of Armstrong Laboratory,
characterizing and modeling the interaction of laser
and other optical radiation with biological systems. His current area of interest
is the physics of laser-induced breakdown in the eye and its relationship to
observed ocular damage from ultrashort pulse exposures.
Dr. Kennedy is a member of Sigma Pi Sigma, APS, and OSA.