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Quasiphase matching of second-harmonic generation in quantum cascade lasers by Stark shift of electronic
resonances
Appl. Phys. Lett. 88, 201108 (2006); 10.1063/1.2203938
Efficient second harmonic generation from large band gap II-VI semiconductor photonic crystal
Appl. Phys. Lett. 87, 131106 (2005); 10.1063/1.2061864
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APPLIED PHYSICS LETTERS 104, 071107 (2014)
(Received 10 December 2013; accepted 3 February 2014; published online 20 February 2014)
A simple experimental method for determining the efficiency of second harmonic generation
(SHG) using small amounts of dry crystalline powder is described. Contrary to previous
techniques, the light scattering effects are explicitly accounted for, and a procedure to eliminate
their influence is proposed. The method also permits to assess whether a particular crystal is phase
matchable or not. Second-order susceptibility coefficients of eight relevant materials for SHG are
determined, and the agreement with the single-crystal data is, in general, fairly good. For
polycrystalline ZnSe samples, a situation of the so-called random quasiphase matching is
evidenced. V C 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4866160]
Recently, the Kurtz-Perry method1 for assessing the effi- function of the second-order susceptibility coefficients dij
ciency of second-harmonic generation (SHG) in powder and refractive indices (G(r) is proportional to g(r)/r in Eq.
samples has been subjected to criticism.2 Most of the objec- (38) of Ref. 2), and S(r,f) accounts for the light scattering
tions derive from the lack of consideration in the theory of effects. In its turn, S(r,f) is a complicated function that
the light scattering effects during the SHG process. These involves the grain size, the packing fraction, the sample
effects are very important and can give rise to errors in the thickness, and the refractive indices of the crystal and the
determination of nonlinear optical (NLO) coefficients of up medium where the powder is immersed (air or
to one order of magnitude. Incorrect conclusions can even be index-matching fluid). The SHG light emitted in the back-
drawn about the very existence of the phase matching (PM) ward or forward directions can be expressed in an analogous
condition in the crystal (see Table V in Ref. 2). Many prob- way by substituting S(r,f) in (1) by the corresponding func-
lems of the measurements of SHG in powders arise from tions for back and forward scattering. Those functions have
oversimplifications of the original Kurtz-Perry method but also been computed in Ref. 2.
are, however, common practices in actual experiments: Lack The key point of the method lies on the fact that, for any
of use of index matching liquid, no control of the powder detection geometry (back, forward, or integrated), the SHG
packing fraction, omission of the influence of the refractive signal can be factored as a part due to the scattering and
indices in the SHG magnitude, or collection of only a (non- another term, G(r), where all the NLO parameters are con-
representative) fraction of the total scattered SHG signal. As tained. Usually SHG measurements are carried out as a func-
a result of these factors, many of the experimental works that tion of r. Thus, it is impossible to make a measurement
make use of the Kurtz-Perry technique are of scarce value without simultaneously altering the scattering effects and the
and should be revised. NLO response. The separation, however, can be worked out
In this paper, we propose an alternative technique to with a two-component sample. A similar idea was proposed
obtain quantitatively the efficiency for SHG in powders. The some years ago,4 with only partial success. In our samples,
method is based on the theory developed in Ref. 2 and con- the test material was prepared as powder of different grain
siders the light scattering by the powder particles explicitly. size and was uniformly mixed at low concentration (about
In contrast with other procedures that use samples in the 1% w/w) in a matrix inert from the point of view of NLO.
form of powder crystal monolayers,3 the method is not As a matrix, we used glass spheres of 100 lm of diameter
affected by possible preferential orientations of the powder (Cospheric). In this kind of samples, the NLO effect arises
particles on a surface. It is not necessary to use any index from the test material, while the scattering effects are essen-
matching fluid (dry powder) and only very small amount of tially due to the glass spheres and can be calibrated easily.
material is required. The method is therefore quite appropri- The SHG signal results
ate for a quick review of the potentialities of NLO materials.
To explain the technique, we start recalling that the I2 fm GrSrg ; fg I1 2 ; (2)
SHG by a powder sample can be formally written as2
where fm and fg are the volume packing fraction of the active
I2 fGr Sr; f I1 2 ; (1) material and glass, respectively, and rg is the diameter of the
glass spheres.
where I2 is the total integrated SHG flux, I1 is the intensity of If the size and packing fraction of the glass particles are
the fundamental beam, f is the volume packing fraction, and constant, the scattering function is also a constant, and the
r is the particle size of the crystalline powder. G(r) is a NLO efficiencies can be deduced straightforwardly if SHG
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071107-2 Aramburu et al. Appl. Phys. Lett. 104, 071107 (2014)
TABLE I. Second-order susceptibility coefficients of some relevant crystals for SHG at k 1064 nm. The refractive indices were taken from: Ref. 14 (quartz),
Ref. 15 (KDP and ADP), Ref. 16 (urea), Ref. 8 (POM), Ref. 17 (BBO), Ref. 18 (KTP), and Ref. 19 (ZnSe).
I2sat
Material Point group I2sat KDP
dij (pm/V)a dij (pm/V)b dij (pm/V)c
a
This work.
b
Recommended value.
c
Further references.
d
Measured at k 600 nm.
e
The modern reference d11(quartz) 0.30 pm/V was adopted.
f
The old reference d11(quartz) 0.50 pm/V, used in the original work, was maintained.
g
d31 and d33 were assumed negligible according to Ref. 5.
h
deff for KTP was defined as the square root of the ratio of the SHG intensities of KTP and KDP, multiplied by d14(KDP). deff is a complicated function of d31,
d32, d33, and the refractive indices.
we obtain d14(KDP) 0.35 pm/V, in good agreement with is a real situation of PM. This PM condition is unusual and is
the data from the literature. called random quasi-phase matching (RQPM).20,21 It can be
Other crystals were also studied and the results are col- attained in highly transparent polycrystalline cubic samples.
lected in Table I. Only commercially available materials We obtained the ZnSe crystalline powder by crushing a
with technological interest for which there exists a reasona- sheet of chemically vapor deposited ZnSe, supplied by
ble consensus about their dij coefficients were selected. Aldrich. Contrary to our initial assumption, we found that
Except for quartz and ZnSe, all are phase matchable, and the the powder particles themselves were, in fact, polycrystalline
dij coefficients were deduced using just the asymptotic value (see Fig. 4). The presence of domains oriented randomly is a
of the SHG intensity (I2sat ) (in general, I2 vs. r is essentially a basic requirement for the RQPM to occur. In addition, the re-
constant in these materials). The literature values for dij (fifth fractive indices must not show any jump between adjacent
column of Table I) are those most commonly accepted domains to avoid scattering losses and permit a high SHG ef-
among researches. When possible, the recommended stand- ficiency. That condition occurs automatically in cubic crys-
ards of the NLO coefficients have been given.5 In the cases tals because the indices are isotropic and polarization
of discrepancies, additional references have been provided
which show better accordance with our results. The agree-
ment is in general fairly good.
ZnSe deserves a separate mention. This material is cubic
(crystal class 43m). The function g(r) can be shown to be
given by
8d142
sin2 Dkr=2
g r ; (3)
7e0 cn2 n21 n2 n1 2
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071107-4 Aramburu et al. Appl. Phys. Lett. 104, 071107 (2014)
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