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Electro-optic, linear, and nonlinear

optical properties of KDP and its
isomorphs
a
D. Eimerl
a
University of California, Lawrence Livermore National
Laboratory, Nonlinear Optical Materials Group, P.O. Box
5508, Livermore, California, 94550
Version of record first published: 08 Feb 2011
To cite this article: D. Eimerl (1987): Electro-optic, linear, and nonlinear optical properties of
KDP and its isomorphs, Ferroelectrics, 72:1, 95-139
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Ferroelecm’cs, 1987, Vol. 72, pp. 95-139 01987 Gordon and Breach Science Publishers S.A.
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ELECTRO-OPTIC, LINEAR, AND NONLINEAR

OPTICAL PROPERTIES OF KDP AND
ITS 1SOMORPHS-f
D. EIMERL
University of California, Lawrence Livermore National Laboratory, Nonlinear
Optical Materials Group, P . 0. Box 5508, Livermore, California 94550
Downloaded by [McGill University Library] at 02:33 26 July 2012
(Received April 17, 1986)
The electro-optic, linear, and nonlinear optical properties of KDP and its isomorphs are reviewed.
Figures of merit for doubling and tripling by sum-frequency generation are presented and used to
compare and contrast these crystals for nonlinear optics devices. Current research areas, such as
high-average-power applications, and optical damage resistance are reviewed.
HISTORICAL INTRODUCIION
The very first materials to be used and exploited for their nonlinear optical and
electro-optic properties were potassium dihydrogen phosphate (KDP) and
ammonium dihydrogen phosphate (ADP). They were used in the first experi-
ments in nonlinear optics, and together with their isomorphs, they are still used
widely in nonlinear optics devices. They also continue to be popular as
electro-optic materials. The development of electro-optic and nonlinear optical
devices is intimately connected with the properties and utility of this series of
crystals.
The first studies of the linear electro-optic effect date back to the latter part of
the nineteenth century, but the field of nonlinear optics began comparatively
recently in 1961 with the demonstration by Franken of second harmonic
generation in a quartz crystal [61Fr]. The observed conversion efficiency was very
small because the process was not phase-matched. Dramatic increases in the
conversion efficiency were soon obtained using the then new technique of
phase-matched harmonic generation [62Ma], [62Gi] in ammonium dihydrogen
phosphate (ADP). Refinements of the technique increased the conversion
efficiency to 50% and greater, and harmonic generation was established as an
important and practical tool for extending the frequencies available at the
intensities available in pulsed lasers. KDP became popular as well because it was
more transparent in the near infrared than ADP.
The usefulness of the KDP isomorphs is due largely to the ease with which
large, high optical quality crystals can be grown. Their ready availability
stimulated both fundamental research and the development of devices exploiting
their unique properties. Because they have moderately high birefringence,
t Work performed by Lawrence Livermore National Laboratory under the auspices of the U.S.
Department of Energy under Contract W-7405-Eng-48.
95/[397]
96/[ 3981 D. EIMERL
adequate nonlinear and electro-optic coefficients, and are quite resistant to high
intensity optical damage, they are well suited for applications involving high
power lasers. The symbiotic relationship between the (then) emerging fields of
nonlinear optics and electro-optics on the one hand, and high power lasers on the
other, aided the development of both technologies. This symbiosis is still evident
today in the development of short wavelength lasers for fusion. Boules of KDP
are being grown in dimensions of 40cm x 40cm x l00cm (Figure 1) and
fabricated into arrays containing nine 27 cm x 27 cm x 1.2 cm plates (Figure 2).
These arrays are used to frequency-convert high-power fusion lasers from a
wavelength of 1064 nm to the second and third harmonics at 532 nm and 355 nm.
The laser beam aperture is 90cm, and the conversion efficiencies achieved are
FIGURE 1 B o d e of KDP grown at Cleveland Crystals, Inc. for Lawrence Livermore National
Laboratory’s Laser fusion program.
ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP [399]/97
FIGURE l(b)
7O-80%. The size of available high quality crystals has increased substantially
over the first crystals used in nonlinear optics. Yet these crystals almost certainly
do not represent the limits on crystal growth technology.
Research on techniques and materials for efficient frequency conversion has
been pursued more or less continuously in the 25 years since Franken's first
experiment, and it continues to be a subject of active research. Work on
techniques such as sum and difference frequency generation and the design of
nonlinear and electro-optic devices continues, with the modern emphasis shifting
to high average power devices which can handle the thermal loads involved. The
most recent development in efficient frequency doubling techniques is the
quadrature system [84Ei], which was first demonstrated using deuterated KDP
and is capable of over 95% conversion efficiency.
In this paper, the properties of KDP and its isomorphs are reviewed with
respect t o electro-optic and nonlinear optic devices. The emphasis is on the
relevant materials properties rather than on the design of the devices themselves.
To keep the list of references manageable, the references list mostly those papers
with materials properties data, and only a few reports of applications are
included. I trust that the interested reader will find the listed references useful as
a starting point for a deeper survey of the literature on these crystals.
D. EIMERL
FIGURE 2 Frequency conversion array for the 90-cm aperture NOVA laser system at Lawrence
Livermore National Laboratory.
LINEAR OPTICAL PROPERTIES
The refractive index is perhaps the most fundamental optical constant of a

transparent material. In the case of a harmonic generating material, accurate
absolute values are essential in order to predict phase matching directions in the
crystal. It is therefore surprising that with the exception of KDP and ADP,
accurate index data spanning the entire region of transparency is not available.
The refractive indices of KDP and ADP were measured accurately in the
region of transparencies by Zernike in 1964 [ M E ] . This data remains the most
complete and precise of any refractive index data on the KDP isomorphs.
Virtually no new data was published until 1982 when single-pole Sellmeier
parameters were given for nine isomorphs by Barnes, Gettemy, and Adhav
[82Ba], based on data taken between 410 and 650 nm. More recently, double-pole
Sellmeier parameters were given by Kirby, Hoeffer, and DeShazer in 1985 [85Ki].
Their data spans the region from 400nm to 1064nm and includes 13 isomorphs
(all except KD*A). Their data was fit to a double-pole Sellmeier formula:
n2 - 1= A + & / ( l - (A,/A)2) + &/(A2 - A:) (1)
The parameters are given in Table I. The parameters given by Zernike and
Barnes are presented in Tables I1 and 111.
1ABLE I
Sellmeier parameters of Kirby ei al.
-
A 4 A, B2 12
KDP
ord 1.257574 1.76225 7.609065 0.010115 0.118982
ex1 1.129495 0.752775 11.27179 0.009650 0.037136
KD'P
ord 1.240921 2.246956 11.26591 0.009676 0.124981
ext 1.126019 0.784404 11.10871 0.008578 0.109505
KDA
ord 1.424647 3.742954 11.26515 0.015841 0.13647
ext 1.262579 0.769288 11.27181 0.013461 0.127145
ADP
ord 1.301929 1.78281 6.840459 0.010569 0.133602

ext 1.162273 1.823756 11.31744 0.009866 0.101736
AD*P
ord 1.279481 1.215879 7.614168 0.010761 0.115165
ext I . I51161 1.199009 11.25169 0.009652 0.W85.5
ADA
ord 1.443449 2.017752 7.604942 0.016757 0.135177
ext 1.275962 1.59826 11.26433 0.014296 0.128689
AD*A
ord 1.413739 1.036935 7.71675 0.019040 0.49262
ext 1.259082 0.187187 6.447657 0.01m2 0.05 1293
RDP
ord 1.249885 3.688005 11.27829 0.01056 0.088207
ext 1.159913 0.988431 1l.3OOl3 0.009515 0.092076
RD*P
ord 1.235596 2.355322 11.26298 0.010929 0.0376136
ext 1.152727 0.691253 11.27007 0.010022 0.037137
RDA
ord 1.3!30661 3.487176 11.25899 0.015513 0.134582
ext 1.27557 0.720099 11.25304 0.013915 0.1208
RD*A
ord 1.373255 1.979528 11.26884 0.01543 0.125845
ext 1.270806 0.275372 7.621351 0.013592 0.126357
CDA
ord 1.420405 1.403336 7.60422 0.016272 0.134185
ext 1.350262 0.685328 11.28135 0.015645 0.121741
CD*A
ord 1.40817 2.212173 11.26371 0.015598 0.138209
ext 1.345809 0.651843 11.28408 0.015141 0.129754
TABLE I1
Sellmeier parameters of Zernikc
A 4 A, B2 A2
KDP
ord 1.260476 12.99707 20 1.011279(-2) 0.1137646
ext 1.133831 3.227935 20 8.653247(-3) 0.110875
ADP
ord 1.304124 15.10857 20 1.114254(-2) 0.1151979
ext 1.164256 5.805704 20 9.687319(-3) 0.1133888
100/[402] D. EIMERL
TABLE 111
Sellmeier parameters of Barnes
KDP 1.24361 0.00959 1.12854 0.00841

KD*P 1.23318 0.00931 1.12354 0.00828
KDA 1.41427 O.OO990 1.25953 0.01108
ADP 1.28196 0.01069 1.15607 0.00890
ADA 1.42940 0.01341 1.27062 0.01178
RDP 1.23639 0.01059 1.15567 0.00962
RDA 1.37723 0.01301 1.27283 0.01157
CDA 1.40840 0.01299 1.34731 0.01185
CD*A 1.39961 0.01156 1.34417 0.01155
n2 - 1 = B/(1- C/A2)
The temperature dependence of the indices of KDP, KD*P, and ADP was
measured in 1966 by Phillips [66Ph]. Data was taken between 150 and 298 K from
360 nm to 690 nm and was fit to the form
n ( T ) - n(298) = cf(n) - (298 - T ) (2)
+ +
where f = n2 a . n b, and T is the absolute temperature. About the same
time, Yamazaki and Ogawa [66Ya] reported measurements between 100 and
300 K for KDP and 150 and 300 K for ADP and KD*P. They used a fit of the
form
(n - n3m) = A + BT + CT2 (3)
In 1982, Ghosh and Bhar [82Gh] reported double-pole Sellmeier fits to the
indices of KDP, ADP, and KD*P and represented each of the four Sellmeier
parameters as varying linearly with temperature. Data on nine of the isomorphs
in the visible has been given by Barnes et al. Data spanning both the visible and
near-infrared regions was taken for 13 isomorphs (all except KD*A) by Hoeffer
[85Ki], using a new method based on a double interferometer (Figures 3 and 4).
It indicates that the thermo-optic coefficients wn = l / n - d n / d T vary strongly with
wavelength. The dispersion of a;, can be interpreted in terms of the temperature
dependence of the Sellmeier parameters. The refractive index itself is a slowly
varying function of wavelength. On differentiating Equation (1) with respect to
temperature, the terms in d B / d T will also show weak dispersion comparable to
the index dispersion. But the terms in dA/dT will show increased dispersion,
which is more pronounced in the infrared and ultraviolet, and less so in the
visible. This is consistent with the general behavior seen in Figures 3 and 4. The
dispersion of the thermo-optic coefficients is important in evaluating the
temperature sensitivity of harmonic generation and other nonlinear optical
processes. This involves combinations of the thermo-optic coefficients at the
relevant frequencies; it is not sufficient to estimate the temperature sensitivity
using the temperature derivative of the birefringence at a single wavelength. Such
estimates will be accurate only to within a factor of two or three, as in, for
example, the calculations of Barnes et al. The thermo-optic coefficients are not
known precisely enough to calculate the temperature sensitivities accurately.
KD*P-- - ------s
AD'P ___
-20 -00-
-25 -25
-30 -30
-35 -35
200 600 1000 1400 2 0 0 600 1000 1400
Wavelength lnml Wavelength (nm)
10
2 -20
-25
-30
-35 -35
200 600 1000 1400 200 600 1000 1400
Wavelength lnml Wavelength lnml
FIGURE 3 Thermo-optic coefficients a;, = l/n . dn/dT for KDP isomorphs. Data taken by Hoeffer
and reported in [85Ki]. Circles: ordinary index, triangles: extraordinary index.
For each set of index data, the wavelength at which noncritical phase-matching
(NCPM) occurs has been calculated by this author. (Noncritical phase-matching
occurs for a phase-matching angle of 90" [73Ze]). The results for second harmonic
generation are given in Table IV, and for third harmonic generation by
sum-frequency mixing of the first and second harmonics in Table V. Overall, the
agreement between calculated and observed wavelengths is quite good. A large
part of the discrepancies can reasonably be attributed to extrapolation errors.
However, the index data is not yet complete enough to perform reliable
""
200 600 1000 1400
:::I,
-35
200
,
600 1000 1 0
Wavelength (nm) Wavelength Inm)
t -5
-30
-35
200
u 600 1000 1400
Wavelength lnml
FIGURE 4 Thermo-optic coefficients an= l / n . d n / d T for KDP isomorphs. Data taken by Hoeffer
and reported in [85Ki]. Circles: ordinary index, triangles: extraordinary index.
TABLE IV
Second harmonic noncritical wavelength of KDP isomorphs
Kirby et al. Eimerl Barnes et al. Zemike
Type I 11 I I1 I I1 I I1 Data (Type I, 20°C)

KDP 487 728 542 739 519 721 518 732 517 518 518
KD*P 531 742 530 739 526 731 519 526 530
ADP 520 756 544 759 514 716 524 751 524 524
AD*P 523 742 526 743 528
RDP 625 1043 635 1041 662 924 626 626
RD*P 626 982 646 991
KDA 573 801 616 831 570 775 596 596
KD*A 610 610
ADA 583 830 591 831 562 777 582 582

AD*A 563 826 584 827 585
RDA 680 1037 679 1034 672 938 684 684
RD*A 699 1020 702 1020 699 699
CDA 1066 1063 898 1263 1052 1052
CD’A 1045 1045 941 1316 1037 1037
73Ad 77Br 83Ad
phase-matching calculations (with the exception of KDP and ADP). The extent
to which phase matching calculations are sensitive to extrapolation errors is
demonstrated by comparing Kirby’s data with a second fit to the same data by this
author, using a different functional form:
n 2 - 1 = A +BA2+ CA4+D/(1-(A&)’) (4)
The results of this fit are presented in Table VI. The rms error of this fit is about
5- and its accuracy is comparable to Kirby’s fit. There are nonetheless large
differences between the NCPM wavelengths calculated from the various sets of
Sellmeier parameters. The difference between Barnes’ parameters and Kirby’s
TABLE V
Third harmonic sum frequency generation: noncritical wavelengths
Kirby et al. Eimerl Barnes et al. Zernike
Type I I1 111 I I1 111 I I1 I11 I I1 111
KDP 674 835 784 900 730 874 1253 738 871 -
KD*P 756 897 1524 753 894 1421 741 888 1270
ADP 739 886 786 913 1312 719 861 1248 751 889 -
AD*P 743 890 748 904
RDP 885 1070 911 1077 932 1124 1606
RD*P 878 1084 933 1092 1655
KDA 818 961 896 1012 1566 817 973 1328
KD*A
ADA 833 985 849 993 793 945 1350
AD*A 788 967 1728 827 991
RDA 965 1151 964 1152 945 1138 1680
RD*A 994 1189 1003 1187
CDA 1539 1449 1652 1263 1533
CD*A 1494 1487 1334 1618
ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP [405]/ 103
TABLE VI
Sellmeier parameters (Eimerl)
A B C D Lo
KDP
ord 0.698696 -3.319326 (-2) 7.706707 (-4) 0.5606856 0.1315899
ext 0.7980716 -1.56089 (-2) 3.993255 (-3) 0.33884 0.1498919
KD*P
ord 0.9575554 -2.824391 (-2) 4.977826 (-3) 0.2901391 0.1677494
ext 0.5005779 -1.054063 (-2) 2.243821 (-3) 0.6276034 0.1146988
KDA
ord 0.988413 -5.826141 (-2) 1.409368 (-2) 0.4430935 0.1710929
ext 1.011142 -3.195326 (-2) 1.217516 (-2) 0.2681806 0.1925064
ADP
ord 1.212279 -9.685763 (-2) 3.949124 (-2) 0.1170906 0.2268105

ext 0.7721719 -2.289421 (-2) 4.011002(-3) 0.3957988 0.1468191
AD'P
ord 0.6837559 -2.494824 (-2) 1.62896(-3) 0.5970244 0.1314933
ext -1.261059 -6.219993 (-3) -3.888768 (-3) 2.457582 0.06756204
ADA
ord 0.6949518 -3.912502 (-2) 1.423904(-3) 0.7512926 0.1463746
ext 0.6590986 -1.82173 (-2) 2.559729 (-3) 0.6206193 0.1469737
AD*A
ord 0.5985275 -2.238475 (-2) -3.971065 (-4) 0.8226489 0.1402481
ext -0.1963525 -2.6083% (-4) 3.778224 (-3) 1.455477 0.1025233
RDP
ord 0.7575657 -3.911456 (-2) 4.782302 (-3) 0.4986887 0.1353779
ext 0.719013 -1.525472 (-2) 3.568325 (-3) 0.445821 0.1368467
RD*P
ord 1.078599 -4.688584(-2) 1.31273 (-2) 0.1757441 0.1950575
ext 0.9321829 -2.855236 (-2) 1.112833 (-2) 0.2353148 0.1699913
RDA
ord 0.6392251 -2.972298 (-2) 8.221364 (-4) 0.7529543 0.1417942
ext 0.09150814 -1.356935 (-3) -2.216456 (-3) 0.181453 0.110563
RD*A
ord 0.7513291 -2.422665 (-2) 4.050693 (-3) 0.6275434 0.1500852
ext 0.7514402 -1.399107 (-2) 4.420164 (-3) 0.5252715 0.1529068
CDA
ord 0.8776328 -3.602222 (-2) 5.234121 (-3) 0.5503951 0.16257
ext 0.6862889 -1.372244 (-2) 3.948463 (-3) 0.6694571 0.1464712
CD*A
ord 0.6278496 -1.822031 (-2) 2.813331 (-4) 0.780817 0.1407699
ext 0.6236063 -9.338692 (-3) 1.965413 (-3) 0.7249589 0.141485
data is perhaps due to difference in wavelength range spanned by the data, but
the differences between Kirby's fit and a second fit to the same data are entirely a
result of extrapolation errors. They can lead to a large uncertainty in the NCPM
wavelength (10-20 nm). Clearly, accurate phase-matching calculations require
precise data (an < 5 spanning the entire range of transparency of the
crystals.
On the other hand, there also appear to be discrepancies in the experimentally
determined NCPM wavelengths which are well outside the experimental errors.
The data for KD*P is particularly interesting.
Kirby et a1. hypothesized that there are slight differences in the optical
properties of different samples of the same crystal and that they are due to
104/[4061 D. EIMERL
impurities, defects, or other compositional variations which depend on the growth

conditions. The NCPM wavelength is sensitive to the infrared birefringence and
also to small changes in the Sellmeier poles. The fractional error in the NCPM
wavelength is one-half that of the birefringence. Thus for KD*P, a change in the
birefringence of 0.0008 is sufficient to change the NCPM wavelength by about
10nm. On the other hand, a shift of the UV Sellmeier pole by 2nm would also
shift the NCPM wavelength by 10 nm.
To test this hypothesis, the crystalline cell constants and refractive indices of
several KDP crystals grown in different laboratories were measured and
compared. Among the crystals studied, they found a variation in about 0.01% in
both the crystalline cell constants and the (visible) refractive indices. This is more
than twice their experimental error, and they concluded that these differences
were real. The data is consistent with attributing these differences to a shift of the
UV Sellmeier pole, possibly due to an absorbing metallic ion impurity. This
would imply larger variations in the UV refractive index than in the visible,
perhaps as much as 0.001, and also strong crystal to crystal variations in the UV
absorption and NCPM wavelengths. Thus, the variation in both reported and
calculated NCPM wavelengths may be due in part to significant differences in the
history and genesis of the individual samples measured. This interpretation of the
discrepancies is consistent with the observation that the XY growth of KDP is
sometimes controlled by adding metallic salts to the liquor.
The optical activity of KDP has been measured by Kobayashi et al. [78Ko],
who obtained a value g,, = 2.28 1 at a wavelength of 506 nm.
The linear optical absorption of some of the isomorphs of KDP are presented
in Figures 5-16. The intrinsic UV edge of the isomorphs is about 200nm, but
actual crystals cut off in the region 200-225nm, depending on the density of
Wavelength, nrn
FIGURE 5 Transmission Spectrum of 11 mm sample of KDP, uncorrected for Fresnel losses.

100 I 1 I I I I I I
90 -
80 -
70 -
60-
B
I
g
I
50- KD*P
40-
30 -
20 -
10 -
0.- I I 1 I 1 I I I 1
200 400 600 800 1000 1200 1400 1M)o 1800 2000
FIGURE 6 Transmission Spectrum of 11mm sample of KD*P, uncorrected for Fresnel losses.
100 , I ' I ' I ' I ' I ' I ' I '
80 -
'z
~
,$
60 -
5
L
2U 40- KDA
20 -
200 400 600 800 loo0 1200 1400 1600 1800

Wavelength A nm
FIGURE 7 Transmission Spectrum of 11 mm samples of KDA and KD'A, unpolarized and

uncorrected for Fresnel losses.
absorbing inclusions. The IR edge consists of an edge sometimes accompanied by

a broad shoulder. When present, the shoulder has about the same width (200 nm)
and strength (about 6m-' for the ordinary ray and about 2m-' for the
extraordinary ray) in all isomorphs. The strong rise in absorption in the IR is a
vibrational photon band, and for the arsenates it is further into the IR than for
the phosphates. The broad shoulder leading to it is strongly sensitive to the level
of deuteration in all isomorphs, and is believed to be an overtone of the IR
absorption band of 0-H at 3000-3600cm-'. It can be shifted to the IR by
D. EIMERL
100
I I 1 I I I I I
90 - -
80 -
70 -
.IP 60
-
'L
-
c
50-
40-
a
30 -
20 -
10 -
0-
200 400 600 800 1000 1200 1400 1600 18W 2000
Wavelength, nm
FIGURE 8 Transmission Spectrum of 11mm sample of RDP, unpolarized and uncorrected for
Fresnel losses.
deuteration. The absorption of the ammonium crystals near 1pm is due to an

overtone of the N-H absorption band at 3300 cm-l.
The strong absorption of the KDP isomorphs in the near IR has limited their
usefulness to the visible and near UV. For example, as parametric oscillators or
amplifiers, they are somewhat inefficient because the idler wave cannot lie in the
near IR and therefore does not carry negligible energy.
100-
I I 1 I I I I I
90 - -
80 -
70 -
-
!, 60
E
-E
c
50-
RD*P
$ 40-
a
30 -
20 -
10 -
0 - I I I I I
200 400 600 800 1000 1200 1400 1600 1800 2000
FIGURE 9 Transmission Spectrum of 11mm sample of RD*P, uncorrected for Fresnel losses.
ELECI'RO-OPTIC AND OPTICAL PROPERTIES OF KDP [409]/107
100 I I I I I I I I
Wanelsnph, nm
FIGURE 10 Transmission Spectrum of 11 mm sample of RDA, uncorrected for Fresnel losses.
100, I I I I I 1 I I
I
80 -
70 -
5 60
-
E
-E
L
50 -
40-
0
30 -
20 -
10 -
200 400 600 800 1000 1200 1400 1600 1800 2000
Wsvelsngth, nm
FIGURE 11 Transmission Spectrum of 11 mrn sample of RD*A, uncorrected for Fresnel losses.
NONLINEAR OPTICAL AND ELECTRO-OPTIC PROPERTIES
KDP and its isomorphs are unique among the popular nonlinear materials
because they are readily grown in useful, optically homogeneous sizes with optical
properties which are reproducible from boule to boule. The nonlinear coefficients
of other nonlinear crystals show considerable variation from crystal to crystal,
108/[410] D. EIMERL
100, I I I I I I I I
I
90 - -
80 - lunpolarizedl -
70 - -
c
:. 60 - -
e
5E
L
50- ADP -
-
j 40-
30 - -
20 - -
10 - -
0 I I 1 I I I I
200 400 600 800 1000 1200 1400 1WO 1800 2000
FIGURE 12 Transmission Spectrum of 11 mm sample of ADP, uncorrected for Fresnel losses.
which is not the case for the KDP group. Also, there is better agreement among
the reported values for their nonlinear coefficients that for any other material.
For comparison, we review, very briefly, the properties of other important
nonlinear materials.
Both the refractive indices and the nonlinearity of lithium niobate vary with the
crystal stoichiometry and until recently determinations of its properties, which
100 I I I I
80 -
70 -
= 60-
i
i
$
w
u
50- AD*P
g 40-
&
-
30
\\ 1
2ot
O200 400 600 800 loo0 1200 1400 1600 1800 W
ZMX)
Wavebngth, nm
FIGURE 13 Transmission Spectrum of 11 mm sample of AD*P, uncorrected for Fresnel losses.

ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP (411]/ 109
100 I I I I I I I I
90 - -
80 - -
70 - -
.pP 60 -
-
'B
$ -
e
L
50-
ADA
40- -
0
30 - -
20 - -
10 - -
Or I I I I I I I 4
200 400 600 800 1000 1200 1400 1600 1800 2000
FIGURE 14 Fresnel losses.
involve irradiation with moderately high fluences, were complicated by the

photorefractive effect [78Ra, 82GuI. This situation is improving with the
development of MgO-doped crystals, but historically it has been considered a
disadvantage and has limited its usefulness as a nonlinear material.
Literature values for the nonlinearity of another nonlinear material, lithium
iodate, vary by more than a factor of three [84LB]. This has been attributed in
loo
90
3-
80 -
70 -
6 60-
E
g 50-
L
&
E 40-
30 -
20 -
10 -
200 400 600 800 1000 1200 1400 1600 1800 2000
Wavelength, nm
FIGURE 15 Transmission Spectrum of 11 mm sample of CDA, uncorrected for Fresnel losses.

110/[412] D. EIMERL
100 I I I I I I I I
90 -
80 -
70 -
60-
‘3
‘B
e
w
9.
50-
5 40 -
a.
30 -
20 -
10 -
0
200
1
400
I
600
I
800
I
1000
I
1200
1
1400
I
1600 1800
I
2000
Wavelength, nm
FIGURE 16 Transmission Spectrum of 11 mm sample of CD*A, uncorrected for Fresnel losses.
recent Soviet work to small variations in the crystal chemistry [84Am]. Other
issues with lithium iodate are the existence of another tetragonal phase in
addition to the hexagonal phase, and the relatively low resistance to damage
under intense, short (nsec) pulse irradiation. Recent Soviet work claims that its
damage resistance can be increased by careful attention to the purity of the
crystal [85Vl].
Another promising material, KTiOP04 [76Zu], is not yet available in sufficient
size to obtain precise optical information, but there are indications that its linear
optical properties show significant variation from boule to boule [85Pe].
In contrast, KDP and its isomorphs are considerably more predictable. Such
variations as may exist between boules are barely measurable and are estimated
to be less than 0.03% (see below). Surprisingly, there are very few absolute
determinations of the nonlinear coefficients of the KDP group, and all but three
were made in the 1960s. The early experiments used a focused beam geometry.
Their interpretation is complicated by the effects of beam walk-off and the
nonuniform beam profile at the focus associated with the multimode character of
the lasers. Early measurements on ADP were also complicated by its absorption
near 1064 nm. The most reliable measurements are comparatively recent and use
diffraction-limited or single-mode high energy pulsed lasers to measure the
conversion efficiency of highly collimated beams [85Br, 81Cr2, 82Eil. The
advantages of using a large-aperture, collimated beam with a uniform profile are
several: (1) double refraction, while present, does not affect the conversion
efficiency and can be ignored, (2) there is no diffraction as the beam propagates
through the crystal and therefore the driving terms for the harmonics are spatially
uniform, (3) the beam divergence can be made much less than the angular
acceptance of the crystal and the effects of angular dephasing are simple to
calculate. Ihese “plane-wave” experiments agree closely on the nonlinear
coefficient of KDP, and there is therefore a high degree of confidence in their

mean value:
d36(-20, o,o)= 0.39 f 0.01 pm/V (5)
and
d14/d36 = 1.00 f 0.05 (6)
where w is the frequency of a 1064 nm Nd laser. The definitions of the nonlinear
coefficients we use here are given in the Appendix; unfortunately some recent
papers use a definition which differs by a factor of 2 from the original work. The
large-aperture data on the frequency dependence indicates that
d36(-3W, 2w, o)/d36(-20, 0,w ) = 1f 0.05 (7)
and
d34-4w, 2w, 2 w ) = 0.565 f 0.02 pm/V (8)
The experimental data on the other isomorphs is shown in Table VII. The
data includes both absolute determinations, and also relative determinations of
the coefficients, typically by comparison with d36(DP). The spread in the data is
significantly greater than the probable difference between d14and d36, and so in
compiling this table Kleinman symmetry was assumed. The spread in the data is
due to a number of factors; possibly the most significant factor is the use of
focused beams. More precise determinations of the nonlinear coefficients of the
isomorphs (with the possible exception of ADP) would be of great value, both for
theoretical modeling and for device design.
TABLE VII
NLO coefficient dw of KDP isomorphs
Material 0.532 0.63 - 0.69 1.064 1.15
~ ~~
KDP 0.57 85Br 0.39 69Ha 0.62 63Ash

0.39 8 1 0 1
81Cr2
0.39 85Br
0.39 86Ei
KD*P 0.29 63Mi 0.24 77Re
0.37 68Su 0.36 64Mi
KDA 0.27 68Su 0.41 64Mi
ADP 0.28 76Re 0.42 65Mcl 0.39 63Mi
0.28 66Fr 64Mi
0.29 67Bj 0.47 70Je
0.37 63Mi
0.46 68Su
AD'P 0.43 68Su
RDP 0.35 72Pe 0.40 74Ka
0.40 68Su
RDA 0.4 78Su
0.25 68Su
0.21 72Pe
CDA 0.36 74Kal
0.21 68Su
CD*A
0.36 74Kal
TABLE VIII
Electro-optic and nonlinear optic properties of KDP isomorphs
T T S
r14 r36 r36 "0 "e KL Kr3 d36 46 d36/d;6 a
KDP 8.77 10.3 9.7 1.4938 1.4599 42 21 0.39 0.73 0.54 7.453 6.975 387 2.57 66 15.5 5.82 -150
KD'P 8.8 26.4 24.3 1.4931 1.4582 65 51 0.36 0.74 0.49 7.470 6.977 389 2.39 61 6.1 5.97 -51
KDA 12.5 10.9 1.5477 1so59 54 21 0.27 0.99 0.27 7.630 7.161 417 1.24 29 13.2 6.16 -178
KD'A 19.4 (1.54) (1.51) 70 31 (0.39) 1.16 7.641 7.164 418 7.5 7.31 -114
ADP 25 8.6 5.5 1.5087 1.4680 56 15 0.47 0.91 0.51 7.499 7.549 425 2.82 66 18.0 6.95 -126 P
AD'P 34 11.9 1.5050 1.4660 72 22 0.43 0.84 0.51 7.519 7.540 426 2.64 62 13.1 6.41 -32
ADA 9.2 1.5551 1.5081 75 14 (0.43) 1.32 7.694 7.720 426 15.4 8.00 -57
AD'A 1.5524 1.5059 +29
(0.40)
Em
RDP 9.1 14 12.7 1.4921 1.4696 42 28 0.41 0.75 0.55 7.608 7.296 422 2.65 63 11.4 5.86 -126 T!
RD*P 32 1.4914 1.4682 (0.38) -55
RDA 13 1.5405 1.5105 55 29 0.25 0.84 0.30 7.793 7.467 453 1.16 26 11.2 5.25 - 163
RD'A 22 1.5393 1.5092 72 42 (0.31) 0.96 7.806 7.467 503 6.6 6.07 -100
CDA 17 1.5512 1.5356 58 34 0.31 1.01 0.31 7.985 7.893 503 1.30 26 8.4 5.83 - 130
CD'A 37 1.5500 1.5341 74 61 (0.30) 1.20 0.25 7.985 7.893 503 1.30 (26) 3.9 6.97 -32
The best values for the nonlinear optical coefficients and the electro-optic
coefficients are given in Table VIII, as well as the dielectric constants, refractive
indices, crystal cell dimensions, and Curie temperatures. The difference between
the clamped and unclamped electro-optic coefficients is significant only for the r36
electro-optic tensor component and is apparently smaller than the experimental
error for rI4. This data can be used to investigate various hypotheses about the
frequency dependence of the coefficients and their origin.
The temperature dependence of the electro-optic coefficients is described quite
accurately by the temperature dependence of the dc dielectric constant. Thus the
linear electro-optic coefficient p& varies by less than 10% from room temperature
down to the Curie point. In this temperature range, the electro-optic coefficient
r& obeys a Curie-Weiss law. Table VIII lists the coefficient r& and the Curie
temperature. p& is slightly larger for the arsenates than for the phosphates.
The electro-optic coefficients r36 show a strong dependence on deuteration,
which is shown for KDP and RDP in Figure 16. On the other hand, the &6
coefficients are only weakly dependent on deuteration. The quality K33 (20 - T,)
is independent of deuteration for KDP, KDA, and RDA, but decreases by a
factor of two on complete deuteration for ADP and CDA. For the first three
crystals, the effect of deuteration is merely a shift in the Curie temperature,
whereas for the latter two it also causes a drop of a factor of two in the numerator
of the Curie-Weiss law.
THEORETICAL MODELS
An elementary, semiclassical model of the nonlinear behavior of the crystal views

it as a mechanically constrained assembly of electrical charges. In three
dimensions, its normal modes will involve nonrectilinear motion of the individual
charges. Thus driving charge into forced oscillation along the x-direction causes
charge to oscillate anharmonically in another, by virtue of their mechanical
constraints and coupling. As an example, consider an electron constrained to
move on an arc of a circle. Applying an electric field at frequency w tangentially
to the arc causes the electron to move harmonically in the tangential direction
(the x-direction). Then its motion in the radial direction (y) is necessarily
anharmonic because of the circular constraint. The equation of the arc is
(y - R ) 2 + x 2 - R 2 = 0 (9)
where R is the arc radius. With x = A cos(ot), the motion in y is
y = x2/2R (10)
= A 2 / 2 R * ( 1 / 2 )* [ 1 + ~ 0 ~ ( 2 w t ) ] (11)
In this way, an oscillating dipole moment is set up in the y-direction at the second
harmonic frequency. An equal dipole moment at zero frequency also appears,
because there is a net shift of the electron towards the center of the circle. For the
single electron-arc,
Py(2w)= 1/4eR . (PX(w))’ (12)
114/[416] D. EIMERL
where e is the charge. This dipole will emit radiation at the second harmonic with
a power decreasing as 1/R2.
For an entire crystal filled with such electron-arcs, the corresponding relation
for the dipole moment densities is
PY(24 = gYxxPx(242 (13)
and p is the density.

In this way, the nonlinearity is visualized in terms of a number of electrons per
unit cell of the crystal which respond to sinusoidal electric fields by moving along
paths which are locally curved. For an electron in a PO4 atomic group, this
curved path comes about because the electron is repelled by the negatively
charged oxygen atoms and veers away from them. It is possible to estimate the
curvature, R. Assuming that all the 2p electrons in each PO4 group contribute
and including four groups in each unit cell (volume = 390 A3), the density is
p = 0.062. lo3’ m-3 (15)
and using g = 0.0257 m2/C (see Table VIII), we find
R = 9.9 8,
In other words, the arc radius is about the size of the unit cell.
To make this heuristic model consistent with the known crystal structure (space
group 122) would require an appropriate three-dimensional arrangement of the
arcs and a proper treatment of the associated angular factors; this would clearly
be taking the model too far. Nonetheless, this calculation illustrates the principle
that a semiclassical model of the nonlinearity is consistent with its observed
magnitude and gives a simple picture of harmonic generation and optical
rectification. Levine has developed a more sophisticated model based on
elementary charges and chemical bonds which will be discussed below.
The local electric field inside the crystal is intensified by the polarizability of the
surrounding crystal, and the power radiated is also intensified by the same effect.
Miller [64Mi] made this explicit by writing the nonlinear coefficients as follows:
E,, . d..
ilk = x..x..x
I I 11 kk ‘ 6ijk
(17)
where x is the polarizability for the appropriate frequency and polarization:
xi;= (n: - I) (18)
Robinson [67Ro] has shown that this decomposition of the nonlinear coefficients
can also be viewed as representing the frequency dependence of the microscopic
polarizabilities, with local field effects fully included.
The units of Miller’s coefficient, 6, are m2/C and it describes the free-space
(mechanical) polarizability of the relevant crystal atomic groups (see Table VIII).
On dividing by the cell volume, the polarizability of an “isolated” atomic grouping is
obtained. The reduced Miller’s 6 appears to be the same for all the phosphates
(66 - 10-36/mC), and about 2/5 that value for all the arsenates. It may therefore
be reasonable to assign the nonlinear response entirely to the oxygen tetrahedra

and none to the metal-oxygen bonds. It appears that proximity effects between
the tetrahedra, giving rise to an associated band structure of the electronic
excitations, are either absent, or insignificant, or that they are constant among
crystals with the same pentavalent ion. The nonlinearity of the arsenic tetrahedra
is about 2/5 that of the phosphate tetrahedra, but the disparity in the nonlinearity
of the crystals is somewhat less because of the local field enhancement. The
recognition of the importance of the local field effect and the desirability of high
index materials has been a constant theme in research on other nonlinear
materials.
According to one model of the nonlinearity [64Mi], its frequency dependence is
determined entirely by the three polarizability factors, and the mechanical

polarizability tensor, 6, is independent of frequency. As shown in the Appendix,
this leads to a relation between the electro-optic tensor, the refractive indices,
and the dielectric constants (Equation A14). The coefficient dj, calculated in this
way from the electro-optic tensor rT6 is also tabulated in Table VIII. The ratio of
the calculated and measured coefficients is about 0.5 for phosphates and 0.3 for
arsenates. The discrepancy is evidently due to the neglect of the infrared
resonances in equating Miller’s 6 at 532nm and KHz frequencies. The model
overestimates the harmonic generation coefficient, suggesting that the infrared
resonances contribute with the same sign as the electronic terms, are about the
same as the electronic terms for the phosphates but are about twice as large for
the arsenates. Ward and Franken [63Wa] have examined this relationship in the
context of perturbation theory expressions for these tensors. Their conclusions
are essentially in agreement with this result.
Several theoretical models of the second order tensors have been developed,
including the bond charge model of Levine [73Le] and molecular models
developed for organic crystals. The focus of inorganic theory has been either
binary compounds of the Wurtzite structure, or oxygen tetrahedra ferro-electrics
based on a B 0 6 tetrahedral grouping. Levine has extended the bond model
calculations to crystals of arbitrary space group, and in particular to KDP.
Reasonable agreement with experimental data was obtained. The bond model
assumes that the macroscopic polarizabilities (linear and nonlinear) are associated
with the semiclassical motions of effective charges in individual bonds, i.e., within
binary groupings of the atoms in the crystal. It represents an approximation to the
local electron density and the local potential in the crystal. It shows the
importance of the UV absorption edge, the bond orientation, and the density of
participating electrons (bond charge) in determining the optical properties.
However, the extent to which they include the electronic band structure and local
field effects is unclear, and there is some evidence that groups of more than two
atoms are required to obtain the correct relationship between the components of
the d-tensor [74To, 76Ch, 77Ch, 78Cu, 85Lil. As applied to KDP, they involve
judgement and extrapolation of empirically determined effective parameters from
one material to another. The polarizability of the phosphate group (that is, the
four P-0 bonds) dominates, and it was obtained by extrapolation from A1PO4
and other nonlinear phosphates. The predictions nonetheless have the right sign
and magnitude, to within a factor of two.
116/[418] D. EIMERL
While a full discussion of the theoretical models is beyond the scope of this
review, we note that bond models are an empirical semiclassical approach which
are accurate to within a factor of about two, once the dominant contribution to
the nonlinearity has been identified. However, our theoretical understanding of
nonlinear optical properties and birefringence is insufficient to calculate them for
new materials. For dielectric crystals, the nonlinearity depends on the matrix
elements between excited states in the conduction band. Such matrix elements
are generally known much less accurately than the energy levels, and yet it is not
possible to calculate the UV absorption edge of even simple binary crystals, such
as the alkali halides, without including electron correlations in the conduction
bands [82Ku]. Bond charge models represent an approximation to the general
case but one which cannot be applied without using empirical data. Chen [76Ch,
77Ch, 78Ch, 85LiI has pursued an approach based on molecular radicals to

develop an improved intermediate theoretical model, but this has not yet been
applied to KDP.
HARMONIC GENERATION
Frequency conversion is a highly successful technique for extending the usefulness

of existing lasers. The KDP isomorphs include two of the most commonly used
materials in frequency conversion, KDP and CD*A.
The relevant figure of merit for frequency conversion is the theshold power
(85Ei). Efficient frequency conversion requires that the brightness exceed the
threshold power of the nonlinear material. To fix notation, consider sum
frequency generation, whereby waves of frequency w and f2w are mixed to
generate a wave at o3= (1+f2)w. The nonlinear polarization at w 3 is
P3 = EO 2dec * El& (19)

and the equations for the three fields are
dE,/dz = - .CE,*E3- ePiAkz (20)
d&/dz = -f,.CE:E,. e-iAkz
dEJdz = (I +f,).C&E, - e+IAkZ
It is convenient to normalize the fields in units of GW”2/cm so that the intensity,
I , is EZwith no other factors. Then,
C = 5.456de4pm/V)/ A (pm) (n n2n3)1’2 (23)
is the nonlinearity expressed in units of GW-”’. The phase mismatch Ak is due to
the inevitable slight angular misalignments in the laser beam:
Ak = @SO (24)
The exact solution of these equations gives the conversion efficiency [62Ar]
r j = tanh2[$tanh-1(sn[2rjA’2,1 + S2/4r]o])] (25)

ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP [4 19]/1 17
where sn is a Jacobi elliptic function,
6 = tAkl, (27)
and I is the crystal length. High efficiency requires that 1> qo> 5 , and that
161 <0.3 (85Ei).
Consider laser a beam propagating in the z-direction, with a rectangular cross
section of dimensions H and H' in the x- and y-directions. The dephasing Ak
depends only on the beam divergence in one plane (xz or yz) but not on both.
Taking this plane to be the xz plane, the relevant beam divergence is:
68 = QA/H (28)
where Q is the etendu, that is, the number of times the beam divergence in this
plane is greater than that of a diffraction limited beam of the same aperture.
Eliminating I from 26 and 27, we find
qo/4d2 = P/&Q2 * ( H ' / H ) (29)

where P is the total power, (Z2 + Z,)HH', and the threshold power is
Clearly, efficient conversion requires that P / Q 2 exceed a threshold given

approximately by the threshold power. The threshold power also is a useful
parameter for ranking nonlinear materials; the material with the lower threshold
power is considered superior. A more complete discussion of this figure of merit
and the aperture scaling laws of harmonic generators is given in reference 85Ei.
The parameters of the KDP isomorphs for doubling 1064 nm are given in Table
X, and their parameters for mixing 1064 and 532nm to generate the third
harmonic are given in Table XI. (The indices at the relevant wavelengths are
given in Table IX.) Parameters for doubling 532.1 nm and 526.0nm, based on
Zernike's index data and using the known dispersion of the nonlinear coefficient,
are given in Table XII.
Calculations of the phase matching angles and the angular sensitivity for all the
isomorphs except KD*A have been carried out by this author for doubling and
tripling (by sum frequency mixing the first and second harmonics). These
calculations are based on Kirby's index data, and the results are presented in
Figures 18-29. The nonlinear couplings were taken from Table VIIC, and were
assumed to have no dispersion. This is probably a good approximation for
processes which do not generate light below about 300 nm.
In general, the most useful isomorph for a particular application will have the
lowest threshold power. The threshold power for second harmonic generation is
plotted against wavelength in Figures 30 and 31, and for third harmonic
generation by mixing in Figures 32 and 33. For type I phase-matching, the
threshold rises almost linearly from zero at the noncritical wavelength, with a
slope proportional to where An is the birefringence. It varies
approximately inversely as cos2(0,,), where 8,, is the phase-matching angle. For
type-I1 phase-matching the threshold power is finite (i.e., nonzero) at the
118/[420] D. EIMERL
TABLE IX
Calculated refractive indices at the harmonics of Nd :YAG
4w 30 20 1W
KDP
ord 1.560145 1.531114 1.512125 1.493807
ext 1SO6028 1.485358 1.470396 1.459882
KD*P
ord 1.554054 1.525282 1.507339 1.493102
ext 1.507144 1.483432 1.468283 1.458221
KDA
ord 1.648113 1S99591 1.570404 1.547632
ext 1.583861 1.544202 1.520291 1.505894
ADP
ord 1.580791 1.547578 1.526734 1SO5719

ext 1.524636 1.498635 1.481351 1.467922
AD*P
ord 1.570056 1S40268 1.520983 1SO4949
ext 1.519388 1.494352 1.477760 1.465925
ADA
ord 1.661352 1.610848 1.580123 1.555052
ext 1.593341 1SO872 1.525129 1.508105
AD*A
ord 1.640443 1.601821 1.573727 1.552574
ext 1.579521 1S45680 1.521568 1.506015
RDP
ord 1.554169 1S28293 1SO9970 1.492026
ext 1S20552 1.496667 1.480662 1.469535
RD*P
ord 1S46529 1S23506 1SO6359 1.491322
ext 1.515503 1.494179 1.478768 1.468117
RDA
ord 1.638060 1.590975 1S62495 1.540502
ext 1.588335 1S49174 1.525049 1.510470
RD*A
ord 1.628795 1.584792 1.557741 1.539240
ext 1.586955 1.547230 1.523264 1SO9140
CDA
ord 1.651365 1.602576 1.573174 1.551442
ext 1.621559 1.578136 1.551465 1.535613
CD*A
ord 1.645827 1.597533 1.569171 1.549921
ext 1.620531 1.576096 1.549586 1.534122
noncritical wavelength and rises with wavelength approximately as A’. These

graphs indicate clearly the relative performance of the different crystals in
doubling and in tripling by mixing. They show that if a type-I1 configuration is
phase-matchable, it will have a lower threshold power than the type-I
configuration.
The threshold power for a type-I1 process is finite at the noncritical wavelength
because both the nonlinear coupling and the angular sensitivity vanish there, but
with a finite ratio. Close to noncritical phase-matching, the nonlinearity is very
small and the crystal thickness required for efficient conversion can be very large.
It is therefore relatively unattractive to operate a type-I1 doubler or mixer close
to noncritical phase-matching. The wavelength range over which this occurs is
that for which the phase-matching angle is above about 80°, and is typically quite
TABLE X
Parameters for doubling 1064nm
Type I
KDP 40.90 4.9049 0.2553 0.717 529
KD*P 36.60 4.4646 0.2146 0.6032 620
KDA 41.69 5.9084 0.1795 0.4781 1728
ADP 42.24 5.3553 0.3159 0.8767 422
AD*P 36.70 4.9234 0.2569 0.7135 539
ADA 41.71 6.4867 0.2661 0.7037 961
AD*A 38.85 6.0798 0.232 0.615 1106
RDP 51.08 3.3622 0.3189 0.8973 158
RD*P 47.19 3.2416 0.2787 0.7847 193
RDA 49.52 4.3413 0.1901 0.5098 820

RD*A 46.62 4.0564 0.1671 0.4487 925
CDA no pm
CD*A 82.41 0.5944 0.2973 0.7901 6
Type I1
KDP 58.72 2.524 0.3464 0.9844 74
KD*P 53.67 2.39 0.3436 0.977 67
KDA 61.29 2.8035 0.2275 0.6156 234
ADP 62.38 2.4775 0.3861 1.0878 58
AD*P 54.46 2.5629 0.4068 1.1448 56
ADA 62.43 2.9257 0.3282 0.8838 124
AD'A 58.16 2.9554 0.3317 0.8939 123
RDP 85.27 0.3374 0.0674 0.1918 35
RD*P 75.67 0.8766 0.1822 0.5187 32
RDA 81.81 0.7136 0.0705 0.1918 156
RD*A 77.16 0.9545 0.0960 0.2712 140
CDA no pm
CD*A no pm
(deg) cm-'/mrad pm/V GW-l" MW
small, a few tens of nanometers. Type-I1 phase-matching is problematic in this

way only very close to the noncritical wavelength.
Figures 30-33 can be used to determine the best materials for working with Nd
lasers. The best material for doubling Nd lasers appears to be CD*A. Its figure of
merit is low for critical phase-matching at room temperature and its noncritical
wavelength has been determined experimentally to match the Nd :YAG wave-
length at 112" [73Ad]. The next best materials are RDP and RD*P, followed by
KDP and KD*P. The ammonium crystals absorb too strongly at 1064nm to be
useful at that wavelength. The deuterated crystals are slightly preferred because
their temperature sensitivities are slightly lower, and the protonated crystals have
a weak absorption. For tripling 1064nm, RDP and RD*P are best, followed by
the potassium crystals. For quadrupling (doubling the second harmonic at
532 nm), the only phase-matchable materials are KDP, KD*P, and ADP. ADP is
noncritically phase-matched for doubling 532.1 nm at about 50", where the actual
temperature depends somewhat on the crystal purity. KD*P is known to be
phase-matchable at 532.1 nm with a phase-matching angle somewhat above 80°,
but this depends on the level of deuteration. There is some disagreement in the
120/[422] D. EIMERL
TABLE XI
Parameters for tripling 1064 nm by sum-frequency generation
Type I
KDP 47.13 7.8574 0.2858 1.1237 553
KD*P 46.82 7.237 0.2625 1.0352 553
KDA 53.86 8.9268 0.218 0.8112 1370
ADP 48.28 8.3264 0.3508 1.361 423
AD*P 46.62 7.9284 0.3125 1.2168 480
ADA 53.05 9.7239 0.3196 1.1793 769
AD*A 51.55 9.3067 0.2897 1.0738 850
RDP 60.86 4.5762 0.3581 1.4108 119
RD'P 60.01 4.3443 0.3291 1.2995 126

RDA 67.35 4.9731 0.2307 0.8647 374
RD'A 69.79 4.0988 0.2158 0.8114 288
Type I1
KDP 57.97 5.3687 0.3507 1.3942 167
KD'P 59.50 4.5822 0.3149 1.2565 150
KDA 69.81 4.5571 0.1749 0.6613 537
ADP 60.46 5.3764 0.4032 1.5846 130
AD*P 59.61 4.9676 0.3753 1.4806 127
ADA 69.31 4.9574 0.2644 0.9932 282
AD'A 67.90 4.8159 0.2579 0.9727 277
(deg) cm-'/mrad pm/V GW-"* MW
TABLE XI1
Predictions for 4w from Zernike's data
A = 1.0642
deb C
KDPa 76.76 4.988 0.550 3.03 7.66
ADP~ 80.45 3.9072 0.724 3.93 2.80
(deg) cm-'/mrad pm/V GW-'" MW
A = 1.0532
OPm B deff c eh
KDPa 79.55 4.00 0.555 3.06 4.83

ADP~ 85.3 1.96 0.731 3.97 0.689
~ ~~
(deg) cm-'/mrad pm/V GW-ln MW

"KD'P is similar to ADP but the coupling is smaller by about
2/3; it is also closer to 90" phase-matched, and so it is less angularly
sensitive. Pth for KD*P depends on deuteration level, Pth 5 M W . -
AD'P is not phase-matchable at 0.5321 nm.
ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP (423]/121
40i-----4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x = Deunrallon fraction: MH2,,_xl
02x
FIGURE 17 Effect of Deuteration on the electro-optic coefficient r63 of KDP and RDP. Data taken
from 74W and 71V1.
literature as to whether the refractive indices are linear in the deuteration level
[76Vo] or nonlinear [75V1]. Predicting the phase-matching properties of KD*P
has been hampered by the lack of precise index data in the ultraviolet. Obtaining
this data is certainly complicated by the need to include the deuteration level as
an important system variable. Pure deuterated crystals are apparently more
difficult to grow than the protonated crystals because their solubility is lower, and
they have a phase transition just above room temperature.
For use with Nd lasers, KDP (KD*P) is the most versatile; it is useful in
doubling, tripling, and quadrupling. For both doubling and tripling, RD*P has a
lower threshold power than those of KDP. Both its nonlinearity and its angular
r
70
1
10
0-
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
1
Wavelength, urn
FIGURE 18 Phase-matching angles for second harmonic generation: (a) ADP (I), (b) AD*P (I), (c)
ADP (11), (d) AD*P (11), (e) AD*A (I), ( f ) ADA (I), (g) ADA (11), (h) AD*A (11).
122/[424] D. EIMERL
F -
$
I
30
20 - -
- -
10
1 1 ! 1 1 / I
90 -
50
20
l: 0 L 0.2 0.4 0.6 0.8 1.0 12 14
Wavelength. prn
FIGURE 20 Phase-matching angles for second harmonic generation: (a) KDP (I), (b) KD*P (I), (c)
KD*P (II), (d) KDP (11), (e) KDA (I), (f) KDA (II), (g) CDA (I), (h) CD*A (I).
Wavelength. prn
FIGURE 21 Angular sensitivities for second harmonic generation: (a) ADP (I), (b) AD*P (I), (c)
ADP (11), (d) AD*P (II), (e) ADA (I), (f) ADA (II), (g) AD*A (II), (h) AD*A (11).
i 3
a 2
0 0.2 04 0.6 0.8 1.0 1.2 1.4

Wavelength. pm
FIGURE 22 Angular sensitivities for second harmonic generation: (a) RD*P (I), (b) RDP (I), (c)
RDP (11),(d) RD*P (11), (e) RDA (I), (f) RD*A (I), (g) RDA (11), (h) RD*A (I).
Wavelength. #m
FIGURE 23 Angular sensitivities for second harmonic generation: (a) KDP (I), (b) KD*P (I), (c)
KD*P (II), (d) KDP (11), (e) KDA (I), (f) KDA (11), (g) CDA (I), (h) CD*A (I).
90
80 -
70 -
;6 0 -
p 50-
5
6 40-
::I
B 30-
(L
, , , ,
0
0 02 04 06 08 10 12 14
Wavelength. vm
FIGURE 24 Phase-matching angles for third harmonic generation: (a) ADP (I), (b) AD*P (I), (c)
ADP (11), (d) AD*P (11), (e) ADA (I), (f) AD*A (I), ( 9) ADA (11), (h) AD*A (11).
124/[426] D. EIMERL
90
80 -
70 -
60 -
-
nl
6 50-
nl
5 40-
3e 30-
L
c
20 - -
10 - -
0 - 1 ' ! ' 1 ! 1
-i
70
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Wavelength, prn
FIGURE 26 Phase-matching angles for third harmonic generation: (a) KDP (I), (b) KD*P (I), (c)
KDP (II), (d) KD*P (111, (e) KDA (I), (f) KDA (11), (g) CDA (I), (h) CD*A (I).
.-k 10-
5
5 8 -
6-
4
0'
4-
2 -
0 ! I I 11 111 1 I
Wavelength, pm
FIGURE 27 Angular sensitivities for third harmonic generation: (a) ADP (I), (b) AD*P (I), (c)
ADP (11), (d) AD*P (11), (e) ADA (I), (f) AD'A (I), (g) ADA (11), (h) AD*A (11).
1 I I I I I l
14 - -
eE -
-.
12-
'E 10 - -
-r>
;8 - -
. '$ 6- e -
.
7 10 -
e
E,
i
. 8 -
g 6 -
6
a 4 -
i
2 -
0.2 0.4 0.6 0.8 1.0 1.2 1.4

Wavelength. pm
FIGURE 29 Angular sensitivities for third harmonic generation: (a) KDP (I), (b) KD*P (I), (c)
KDP (11), (d) KD*P (11), (e) KDA (I), (f) KDA (11), (8) CDA (I), (h) CD*A (I).
Fundamental wavelength, pm
FIGURE 30 Threshold power for type I doubling as a function of wavelength.

126/[428] D. EIMEFZL
I I I I I I
O.6 .8 1.0 1.2 1.41.5
Fundamental wavelength, pm
FIGURE 31 Threshold power for type I1 doing as a function of wavelength.
10 1.4 1.8
Fundamental wavelength. pm
FIGURE 32 Threshold power for type I tripling as a function of wavelength.
I I I
6 1.0 1.4 1.8
Fundamental wavelength. pm
FIGURE 33 Threshold power for type I1 tripling as a function of wavelength.

ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP [429]/ 127
sensitivity are somewhat less than KDP’s, and efficient conversion will require
thicker crystals. In applications where volume or weight (and therefore cost) is
significant, such as lasers for fusion, this can be an important consideration. The
best doubler is CD*A, but its temperature sensitivity is somewhat greater than
that of KDP or RD*P. Of the three best crystals, two, KDP and CD*A, are
popular nonlinear materials; the third, RD*P is relatively obscure. The potential
advantages of RD*P over KDP for doubling and tripling may justify further
development and crystal growth studies.
OPTICAL DAMAGE
The threshold for optical damage in high power optical materials is a critical
design parameter, that controls the crystal dimensions needed if the crystal is to
survive without damage. This is particularly important in high energy lasers where
the beam aperture required may be very large.
In general, when an optical material is exposed to very intense light, it may
show many different phenomena, most of which are reversible. These reversible
responses include self-focusing, second harmonic generation, photoacoustic
effects, and photorefractive effects. Irreversible changes may also occur, and
these constitute optical damage. Typically, optical damage in KDP appears to the
eye (under a microscope) as small opaque sites a few microns in size. It may be
found either within the bulk of the crystal or on its surface.
The boundary between reversible and irreversible phenomena is indistinct for
processes whose recovery time is long, or whose effects can be corrected only by
some form of post-irradiation treatment. Photorefractivity is a fluence-dependent
effect which often has a long recovery time and has sometimes been called
photorefractive damage. But it is not a truly irreversible phenomenon, and
therefore is not properly called damage. Another example is solarization, which
appears as a decrease of transmission with increasing fluence. It can sometimes be
corrected by annealing. To the extent that annealing heals the effect, solarization
is not considered to be optical damage because it is not a truly irreversible
phenomenon.
The damage morphology of KDP and its isomorphs is the appearance of
micron-sized isolated opaque sites randomly distributed throughout the volume of
the material. Each site typically shows a highly disturbed central core surrounded
by a radially symmetric strain field containing microcracks which propagate out
from the center. Moreover, further irradiation of the crystal will cause these sites
to increase in both number and size. It is obvious that the energy required to
cause the state of the material at a damage site to change must have been
absorbed from the laser. Evidently, the material contains small, optically invisible
absorbing centers which reach extremely high temperatures and cause the
surrounding material to fracture or undergo chemical decomposition. Damage
requires that the heating due to absorption exceed the cooling due to thermal
diffusion away from the absorbing site. Thermal diffusion gives rise to a
laser-pulse-width dependence of the damage which varies with the size and shape
128/[430] D. EIMERL
of the absorbing center. The precise nature of these absorbing sites is not known
but they could be submicron-size bubbles, impurities, metallic particles, mis-
oriented KDP microcrystallites, bacterial debris, or crystalline imperfections such
as dislocation networks.
From the point of view of damage, a crystal appears before irradiation as a
volumetric distribution of submicron-size absorbing centers of various types and
size. Each site is unique and is characterized by a unique threshold. After
irradiation, only those sites which exceeded their threshold will appear as optical
damage. Damage is therefore a statistical phenomenon which depends on both
the distribution of the threshold over the damage sites and on their volumetric
density. The damage threshold of a given crystal is more a property of the history
of each individual sample and is not a unique property of its chemistry and
structure alone.
In typical samples of KDP and KD*P that are commercially available today, a
fluence of about 7 J/cmP2in a pulse width of 1ns will produce about 100 damage
sites per cm3. For fluences 2-3 times higher, the density is 103-107cm-3. For
fluences about 0.5 of this value, the density is less than 1cm-j. Thus to avoid
optical damage, the fluence must be not more than 3-5 J/cmP3. The damage
fluence appears to vary as a power of the laser pulse width between 0.25 and 0.5.
In all lasers the beam is not uniform across the entuire aperture. To avoid
damage, the most energetic part of the laser aperture must be below the damage
threshold. Therefore, in operating laser systems, the average fluence must be
somewhat less than 3-5 J/cm-2. Thus the aperture for a 1J laser must be greater
than lcm’, but for a 1 M J laser (such as a fusion laser) the aperture needed is
100 m2. The threshold for optical damage is therefore a critical design parameter
which controls the crystal dimensions needed if the crystal is to survive. This has
motivated research directed toward understanding the mechanism of damage in
KDP and increasing the damage fluence.
Attempts to correlate the damage threshold with various pre-irradiation
diagnostics have proved unsuccessful. Endert et al. [77En] examined the relation
between dislocation density and damage threshold and concluded that the
damage threshold was a factor of two larger in regions where the dislocation
density was less than 103cm3. This correlation was not confirmed by Newkirk et
al. (83Ne1, who found no statistically significant correlation between a dislocation
density and damage. Stokowski et al. [81Se] looked for correlations with crystal
growth conditions, dislocations, bubbles, inclusions, microcrystallites, and im-
purities. They noted an unusual annealing effect in which the damage threshold
increased after irradiation with several subthreshold pulses. They found no
statistically significant correlations, and tentatively concluded that damage is
associated with small inclusions less than 0.1 pm in size.
In conclusion, the mechanism of optical damage in KDP is not understood,
although some general conclusions are possible. The initially absorbing sites at
which damage occurs are so small that it is very difficult to observe them before
damage occurs. They are certainly much smaller than the size of the site after
damage has occurred. It is believed that damage is initiated on submicron-size
inclusions of unknown nature.
OTHER NONLINEAR PROPERTIES
Table XI11 lists the two-photon absorption coefficients of several isomorphs at

355 nm and 266 nm. Two-photon absorption is important in the ultraviolet at
266 nm, where it can significantly decrease the conversion efficiency for fourth
harmonic generation, or optical parametric amplifiers pumped at 266 nm. The
absorption at 355nm is effectively too small to cause significant energy loss in
nonlinear devices, but it can make a noticeable difference to thermal effects in
high average power devices. The third-order nonlinear optical susceptibility has
been measured for KDP and ADP. However, direct third harmonic generation
based on x3 (three-photon summation) is inefficient because the relevant
nonlinear coefficients are too small.
TABLE XI11
Two-photon absorption
coefficients*
A 355nm 266nm
KDP 5.9 0.27
KD*P 5.4 0.027
KDA 48
KD*A 27
ADP 6.8 0.24
ADA 35
RDP 50
RDA 59
cm/TW cm/GW
* From 78Li and 86Sm.
The third order susceptibility also gives rise to a dependence of the refractive
index on the intensity. In laser systems, this can cause self-focusing, where the
beam breaks up into a number of small but very intense filaments, and damages
optics. Self-focussing is not seen in efficient harmonic generation experiments in
which 532 nm, 1ns pulses are doubled to 266 nm. The nonlinear refractive index
of KDP has been measured at 1064 nm, but there is some disagreement as to the
correct values. It is between 2.4 lop6and cm*/GW [75Sm, 76Mil.
CURRENT RESEARCH
There has been a steady research interest in the KDP isomorphs, which has
focused on applications rather than on fundamental physical properties. Research
continues on optical damage mechanisms, nonlinear optical processes at high
average power, and engineering new nonlinear materials in the KDP group.
The initial focus of damage studies was the identification of the mechanism of
damage and the nature of the damage sites. However, recent research seeks to
identify correlations between the crystal growth process and the damage
130/[432] D. EIMERL
threshold. Parametric studies by Cooper et al. [86Co] studied the correlation

between pH, cation complexation in the liquor, the solution shear rate, solution
temperature and thermal pretreatment, and the growth of dislocation-free
material. This study is still in progress; the initial indications are that none of
these parameters appears to have a strong correlation with optical damage.
Bacterial debris has been found in the solution and is probably present in the
crystals; however, this has not yet been identified as a significant damage initiator.
Extending nonlinear optical processes to high pulse energy and high average
power was examined by Hon in the mid-1970's [79Ho] and was the focus of a
more recent study by Eimerl [85Ei]. Optical absorption in the nonlinear material
gives rise to thermal gradients which reduce the conversion efficiency by thermal
dephasing and at high repetition rate can cause the crystal to fracture. Achieving
high average power requires careful management of these thermal gradients. The
parameters controlling high average power performance include the temperature
sensitivity, the thermal conductivity, the thermal expansion, and the surface
fracture toughness, in addition to the linear and nonlinear parameters listed
above. They have been measured for KDP and a few other nonlinear materials.
For type-I1 doubling of 1064 nm, the temperature sensitivity of KD*P is
PT = d A k / d T = 54 m-' K-l,
the thermal conductivity is
Kll = 1.86Wm-' K-'
K33= 2.09 Wm-' K-'
and the thermal expansion is
all= 2.49 10-5 K-'
a33= 4.40 10-5 ~ - 1
The fracture toughness measures the resistance of the surface to stress-induced

fracture. Crystal surfaces contain small pits, scratches, and other optically
invisible defects which normally do not affect optical propagation. If the crystal
contains thermal gradients, the nonuniform thermal expansion causes stresses;
the surface microdefects will grow to macroscopic proportions if the surface stress
exceeds a certain threshold. In increasing its size, the defect releases strain in the
surrounding material, and it will grow if the energy required to increase its size is
less than the energy released by the accompanying reduction in strain. If this
occurs, the surface develops large cracks and may become crazed and shatter.
Each surface defect is characterized by its own unique threshold, which
depends on its size. For a defect of linear dimension a, the stress threshold is
S = SO/a1/*
where S, is the surface strength. The surface fractures when the stress exceeds the
threshold of the weakest defect. The surface strength of KDP has been measured
by Marion [85Ma].
-
So = 0.09 MPa m1l2
ELEmO-OPTIC AND OPTICAL PROPERTIES OF KDP [433]/131
Using this data, high average power harmonic generators can be designed and
tested. For devices operating at 1064 nm, KD*P is preferred to KDP because its
absorption is about an order of magnitude smaller. Analysis indicates that the
average power capability of nonlinear materials and processes exceeds the current
state of the art by several orders of magnitude, with careful attention to thermal
management. High average power devices represent a new area of research in
which interest is expected to increase in the near future.
Another area of recent research involves adjusting the refractive indices of a
material to obtain noncritical phase-matching at a specified wavelength. The
index is adjusted either by doping the crystal or by making solid solutions of
structurally similar materials. Thus the lattice constants and the UV absorption
edge can be varied, changing both the birefringence and the wavelength
dispersion of the indices. The KDP group offers an excellent opportunity to test
this idea because of the large number of structurally similar crystals and the range
spanned by their noncritical wavelengths.
The pure crystals show noncritical phase-matching (ncpm) in the range
500-700nm. Presumably a solid solution of two pure isomorphs would show
ncpm at a wavelength intermediate between the ncpm wavelengths of the pure
end-members. By adjusting the composition, the ncpm wavelength would vary
continuously between these two limits. Table XIV shows the tuning range of
ncpm for several solid solutions. The KDP group spans almost the entire range
515-702 nm for doubling and 753-1003 nm for tripling; this includes the
wavelengths of many useful lasers such as dyes and Copper vapor.
Bredikin ef al. [78Br] investigated the dependence of the noncritical wavelength
of KDP on the deuteration level. They found that the NCPM wavelength
increased by about 10nm as the deuteration level increased from zero to 95%.
Their data is in basic agreement with Liu et al. [76Li] who demonstrated that 90%
deuterated KDP is noncritically phase-matched at 61°C. Bredikin et al. [79Br]
also investigated the solid solution K,Rbl-,H2P04 and found that mixed crystals
form only for x > 0.84. The mixed crystal is noncritically phase-matched for
doubling 532 nm at room temperature for x = 0.86.
With the exception of KDP/RDP, all the solid solutions listed in Table XIV
have been found to exist over the entire compositional range between the pure
end-members [84Ei]. The segregation coefficient of As in phosphate crystals is
TABLE XIV
Solid solutions in KDP group.
Doubling Tripling
KDP/RDP 515-529 784-933
KDP/KD*P 515-529 753-784
KDP/KDA 515-616 784-896
RDP/RDA 635-680 911-964
RD*P/ 646-702 933-1003
RD*A 525-590 786-849
ADP/ADA
132/[434] D. EIMERL
about 1.2, and mixed crystals grow quite easily. The segregation coefficient of Rb
in KDP is about 0.15, and it appears that the crystal does not form for Rb
concentrations above about 15 atomic percent, in agreement with Bredikin’s
work. The segregation coefficient for Cs in RDP is very small, about 0.02, and it
appears that Cs-doped crystals also do not form.
It was found that the ncpm wavelength varies nonlinearly with composition.
Nonetheless, the tunability of the ncpm wavelength has been confirmed for
KDP/KDA and ADP/ADA solid solutions. The major uncertainty about these
materials addresses their optical and compositional inhomogeneity . Clearly,
further work on optical characterization is required.
SUMMARY
This review has covered the electro-optic, linear, and nonlinear optical properties
of the KDP group of crystals in their tetragonal, paraelectric phase. The general
properties of the group are established, as are many of the trends in the variation
of these properties among the group members. The properties of KDP, KD*P
and ADP are well established, but this is not true for the other crystals. The
refractive index data does not span the entire range of the transparency; this is
especially relevant for the arsenates in the infrared region above 1000nm. The
data on electro-optic coefficients and dielectric constants is the most complete, but
the nonlinear optical coefficients are not at all well established. This hampers
attempts to compare materials for use in applications; it also precludes testing
theoretical models of the optical properties. Theoretical models and calculations
of the nonlinear properties have been developed and applied to KDP, but not to
other crystals in their group. The properties of the most commonly used crystals
are well established, but the data on the remaining crystals is not complete.
Current research centers on improving their damage threshold, high average
power applications, and on index engineering; however there are apparently no
studies of a more fundamental nature. The KDP group offers a special
opportunity for crystal chemistry studies and research on structure-property
relationships; it is perhaps surprising that they are apparently not the subject of
more basic research.
KDP and its isomorphs were the first materials to be exploited for their
nonlinear and electro-optic properties and they remain the most common
nonlinear materials in current usage. They continue to be useful as research tools
and to offer unique opportunities for more fundamental materials research.
ACKNOWLEDGEMENTS
The author wishes to thank many colleagues throughout the laser and nonlinear optics communities
for stimulating conversations and Alene Clasen for typing the manuscript. This work was performed
under the auspices of the U.S. Department of Energy by the Lawrence Livermore National
Laboratory under contract W-7405-ENG-48.
APPENDIX ON DEFINITIONS
The electro-optic and second-order nonlinear optical effects are described by the
following interaction Hamiltonian.
from which the nonlinear term in the dipole moment density is obtained.
qz,t ) = aHi,,/dEi(Z, t ) (-42)
The Green’s function nonlinear susceptibility x is invariant under time transla-
tions, thus:
Xijk(f1, t2, t 3 ) = Xijk(0, t2 - t3 - ?l)(A3)

It is usual to write the electric field as a sum over discrete frequencies and to
write each frequency component in complex notation:
Each complex amplitude is related to the intensity wave at that frequency as

follows:
= n h JE:J/2R (A6)
where R = 37752 is the impedance of free space and rth is the refractive index for
the appropriate frequency and polarization. On substituting these expressions
into the nonlinear polarization, we obtain
phi =xijk(-wh, of,W g ) E g j E f k * 2ns(wh - wg - 0 , )
(A7)
where the &function derives from the time-translation invariance of the Green’s
function. The nonlinear optical coefficients (d) are related to the nonlinear
susceptibility ( x ) by a factor of two for historical reasons.
dijk = (1/2)Xijk/&O (A81
where E~ is the permittivity of free space ( l / p o c 2 ) .Thus P = 2 ~ ~ and
d Ethe~ units
of d are (pico)meters per volt; some authors quote experimental data for x rather
than d.
The susceptibility is symmetric under simultaneous interchange of two indices
and their associated frequencies. This is a consequence of the CPT invariance of
quantum electrodynamics [79Ei], or equivalently of the form of the interaction
Hamiltonian. In spectral regions far from optical absorptions, the frequency
dependence of the susceptibility is weak. Then, the tensor is symmetric under
interchange of any two indices whose associated frequencies are not separated by
an absorption band (Kleinman symmetry).
134/[436] D. EIMERL
The electro-optic tensor relates the changes in the polarizability to the applied
low-frequency (or dc) electric field. Clearly,
and the electro-optic tensor, r, relates changes in the inverse of the dielectric
tensor to the applied electric field.
In all crystal classes, it is possible to express E-’ as a diagonal matrix, but the
coordinate system in which this occurs (the dielectric or optical coordinate

system) is not in general the same as the crystallographic coordinate system. The
dielectric or optical coordinate system is different from the crystallographic one
only for the triclinic and monoclinic crystal classes. For those classes, it is
necessary to state which coordinate system is being used. In the optical
coordinate system, the electro-optic tensor is related simply to the susceptibility:
) 4dkij(0, - 0 , w ) / [ ~ : ( w )n. ; ( ~ ) ]
r k i j ( ~= (A121
This relation can be used to predict the wavelength dispersion of the susceptibility
and to test certain models of the nonlinearity, such as Miller’s conjecture:
Xijk(W1, WZ, 0 3 ) = ~ii(ol)xjj(~2)~kk(~3)6ijk (A13)
There is some evidence that Miller’s 6 coefficient is independent of frequency
over a wide spectral range, and that materials with different crystal structure and
chemistry possess similar 6 coefficients. This model is used with A12, to relate
electro-optic and second harmonic tensors in Table VIII:
rkij(0) , , o ) [ K k- l ] / [ n 2 , ( 2-
= 4 d k i j ( 2 ~0 ~ )l ] [ n : ( ~ ) n ; ( ~ ) ] (A14)
where K is the dielectric constant.
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69Ha W. F. Hagen and P. C. Magnante, “Efficient second-harmonic generation with diffraction-
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70Je J. Jerphagnon and S. K. Kurtz, “Optical nonlinear susceptibilities: Accurate relative values
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71No W. A. Nordlund, “Absolute signs of the nonlinear optical coefficients of KH,PO,,”
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71Ya J. M. Yarborough and G. A. Massey, “Efficient high-gain parametric generation in ADP
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136/[438] D. EIMERL
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Electro-optic Coefficients
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65Pi Yu. V. Pisarevskii, G. A. Tregubov, and Yu. V. Shaldin, “The Electro-Optical Properties of
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65Va A. S. Vasilevskaya, M. F. Koldobskaya, L. G. Lomova, V. P. Popova, T. A. Regul’skaya, I.
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66so A. S. Sonin, A. S. Vasilevskaya, and B. A. Strukov, “Electro-Optical Properties of
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66Va A. S. Vasilevskaya and A. S. Sonin, “Electro-Optical and Elasto-Optical Properties of
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(1966).
67Va A. S. Vasilevskaya, M. F. Koldobskaya, L. G. Lomova, V. P. Popova, T. A. Regul’skaya, I.
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67Val A. S. Vasilevskaya, S. S. Gorbach, M. F. Koldobskaya, L. I. Kuznetsova, L. G. Lomova, T.
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70Mi J . T. Milek and S. J . Wells, “Linear Electrooptic Modulator Materials,” EPIC, Hughes
Aircraft Company, January, 1970, Report No. AD704556, available from NTIS.
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71Vo E. N. Volkova, B. M. Berezhnoi, A. N. Izraelenko, A. V. Mischenko, and L. N.
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74Ad R. S. Adhav and A. D. Vlassopoulos, “Guide to Efficient Doubling,” Laser Focus
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75v1 0. G. Vlokh, A. S. Krochuk, L. F. Lutsiv-Shumskii, and E. V. Smishko, “Refractive Indices
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85Co Eric Courtens, “Scaling Dielectric data on Rb,-,(NH,),H,PO, Structural Glasses and Their
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Other Nonlinear Coefficients

75Sm W. L. Smith, J. H. Bechtel, and N. Bloembergen “Dielectric breakdown threshold and
nonlinear-refractive index measurements with picosecond laser pulses” Phys Rev. Bl2, 706
(1975).
76Mi D. Milam and M. J. Weber, “Time Resolved Interferometric measurements of the nonlinear
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138/[440] D. EIMERL
78Li P. Liu, W. L. Smith, H. Lotem, J. H. Bechtel, N. Bloembergen & R. S. Adhav, “Absolute

two-photon absorption coefficients at 355 nm and 266 nm”, Phys Rev B17, 4620 (1978).
86Sm W. L. Smith, “Two Photon Absorption in Condensed Media”, CRC Handbook of Laser
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Damage
77En H. Endert, A. Hattenbach, and W. Melle, “Influence of the Real Structure of KDP Crystals
On Their Optical Strength”, Sou. J. Qu. El 7, 1516 (1977).
81Sw J. Swain, S. Stokowski, D. Milam, and F. Rainer, “Improving the Bulk Laser Damage
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Phys Len 40,350 (1981).
82St S . E. Stokowski and J. Swain, LLNL internal report “Interim Report on Laser Damage in
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82Sw J. E. Swain, S. E. Stokowski, D. Milam, and G. C. Kennedy, “The Effect of Baking and
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Phosphate Crystals,” Appl Phys Lett 41, 12 (1982).

83Ne H. Newkirk, J. Swain, S. Stokowski, and D. Milam, “X-ray Topography of Laser-Induced
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86Co J. C. Cooper, “KDP Damage Studies”, LLNL Laser Program Annual Report, UCRL-50021-
86 to be published, available from NTIS.
Solid Solutions
76Vo E. N. Volkova and Sh L. Faerman, “Refractive Indices of KDhH2(,-,~P0, and
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77Br V. I. Bredikin, V. N. Genkin, S. P. Kuznetsov, and M. A. Novikov, “Ninety-degree
phase-matching in KD,H,(,-,~PO, crystals in doubling of the second harmonic of a
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79Br V. 1. Bredikin, G. L. Galushkina, V. N. Genkin, and S. P. Kuzznetsov, ‘‘90” phase-matching
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84Ei D. Eimerl, “New Nonlinear Materials: Index Engineering,” paper presented at Lasers ‘84
conference, proceedings p. 555 (STS press, E. Corcovan, Ed.), 1985.
High Average Power
79Ho D. Hon, “High Average Power, Efficient Second Harmonic Generation”, Laser Handbook
Vol. 3, p. 421 M. L. Stich, Editor (Elsevier North Holland, NY, 1979).
84Ko V. A. Konovalev, A. M. Strel’tsov, and E. A. Shalaev, “Characteristics of Second Harmonic
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Other Materials
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78Ra A. Rauber, “Chemistry and Physics of Lithium Niobate”, Current Topics in Materials
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82Gu P. Gunter, “Holography, Coherent Light Amplification and Optical Phase Conjugation With
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ELECTRO-OPTIC AND OPTICAL PROPERTIES OF KDP I44111139
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Theoretical Models
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Electro-optic, linear, and nonlinear

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ELECTRO-OPTIC, LINEAR, AND NONLINEAR

(Received April 17, 1986)

LINEAR OPTICAL PROPERTIES

The refractive index is perhaps the most fundamental optical constant of a

ord 1.301929 1.78281 6.840459 0.010569 0.133602

KDP 1.24361 0.00959 1.12854 0.00841

Type I 11 I I1 I I1 I I1 Data (Type I, 20°C)

ADA 583 830 591 831 562 777 582 582

ord 1.212279 -9.685763 (-2) 3.949124 (-2) 0.1170906 0.2268105

impurities, defects, or other compositional variations which depend on the growth

FIGURE 5 Transmission Spectrum of 11 mm sample of KDP, uncorrected for Fresnel losses.

100 , I ' I ' I ' I ' I ' I ' I '

200 400 600 800 loo0 1200 1400 1600 1800

FIGURE 7 Transmission Spectrum of 11 mm samples of KDA and KD'A, unpolarized and

absorbing inclusions. The IR edge consists of an edge sometimes accompanied by

deuteration. The absorption of the ammonium crystals near 1pm is due to an

FIGURE 10 Transmission Spectrum of 11 mm sample of RDA, uncorrected for Fresnel losses.

NONLINEAR OPTICAL AND ELECTRO-OPTIC PROPERTIES

FIGURE 12 Transmission Spectrum of 11 mm sample of ADP, uncorrected for Fresnel losses.

FIGURE 13 Transmission Spectrum of 11 mm sample of AD*P, uncorrected for Fresnel losses.

FIGURE 14 Fresnel losses.

involve irradiation with moderately high fluences, were complicated by the

FIGURE 15 Transmission Spectrum of 11 mm sample of CDA, uncorrected for Fresnel losses.

FIGURE 16 Transmission Spectrum of 11 mm sample of CD*A, uncorrected for Fresnel losses.

coefficient of KDP, and there is therefore a high degree of confidence in their

KDP 0.57 85Br 0.39 69Ha 0.62 63Ash

An elementary, semiclassical model of the nonlinear behavior of the crystal views

PY(24 = gYxxPx(242 (13)

and p is the density.

be reasonable to assign the nonlinear response entirely to the oxygen tetrahedra

determined entirely by the three polarizability factors, and the mechanical

77Ch, 78Ch, 85LiI has pursued an approach based on molecular radicals to

Frequency conversion is a highly successful technique for extending the usefulness

P3 = EO 2dec * El& (19)

r j = tanh2[$tanh-1(sn[2rjA’2,1 + S2/4r]o])] (25)

where sn is a Jacobi elliptic function,

qo/4d2 = P/&Q2 * ( H ' / H ) (29)

Clearly, efficient conversion requires that P / Q 2 exceed a threshold given

ord 1.580791 1.547578 1.526734 1SO5719

noncritical wavelength and rises with wavelength approximately as A’. These

RDA 49.52 4.3413 0.1901 0.5098 820

small, a few tens of nanometers. Type-I1 phase-matching is problematic in this

RD'P 60.01 4.3443 0.3291 1.2995 126

(deg) cm-'/mrad pm/V GW-'" MW

KDPa 79.55 4.00 0.555 3.06 4.83

(deg) cm-'/mrad pm/V GW-ln MW

l: 0 L 0.2 0.4 0.6 0.8 1.0 12 14

0 0.2 04 0.6 0.8 1.0 1.2 1.4

0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

0.2 0.4 0.6 0.8 1.0 1.2 1.4

FIGURE 30 Threshold power for type I doubling as a function of wavelength.

FIGURE 31 Threshold power for type I1 doing as a function of wavelength.

FIGURE 32 Threshold power for type I tripling as a function of wavelength.

FIGURE 33 Threshold power for type I1 tripling as a function of wavelength.

OTHER NONLINEAR PROPERTIES

Table XI11 lists the two-photon absorption coefficients of several isomorphs at