crystals

Article
Optical Properties of KTP Crystals and Their
Potential for Terahertz Generation
Alexander Mamrashev 1, * ID , Nazar Nikolaev 1 ID
, Valery Antsygin 1 , Yury Andreev 2,3 ,
Grigory Lanskii 2,3 and Arkady Meshalkin 4
1 Institute of Automation & Electrometry, SB RAS, 1, Ac. Koptyug Ave., Novosibirsk 630090, Russia;
nazar@iae.nsk.su (N.N.); antsigin@iae.nsk.su (V.A.)
2 Institute of Monitoring of Climatic and Ecological Systems, SB RAS, 10/3, Akademicheskii Ave.,
Tomsk 634055, Russia; yuandreev@yandex.ru (Y.A.); lansky@yandex.ru (G.L.)
3 Siberian Physical Technical Institute of Tomsk State University, 1 Novosobornaya Sq., Tomsk 634050, Russia
4 Institute of Thermophysics, SB RAS, 1, Ac. Lavrent’ev Ave., Novosibirsk 630090, Russia; kaplun@itp.nsc.ru
* Correspondence: mamrashev@iae.nsk.su; Tel.: +7-383-330-8378




Received: 30 June 2018; Accepted: 28 July 2018; Published: 31 July 2018


Abstract: High nonlinearity, wide transparency range and optical quality allowed potassium titanyl
phosphate (KTiOPO4 , KTP) crystals to be used in a wide range of nonlinear applications. The success
of KTP usage in the visible and infrared (IR) ranges drives interest in applying it at longer wavelengths,
that is, in the terahertz (THz) range. We use THz optical properties of KTP crystals measured by
terahertz time-domain spectrometer (THz-TDS) and refractive index approximated in the form of
Sellmeier equations to investigate KTP application possibilities for IR-to-THz and THz-to-THz wave
conversion. As a result, phase matching for s − f → f and s − f → s types of difference frequency
generation (DFG) of Ti:Sapphire laser (at the wavelengths of 0.65, 0.8 and 1.1 µm) is found possible,
as well as second harmonic generation (SHG) of THz waves by f + s → f type of interaction in the XZ
principle plane of the crystal. Terahertz wave generation by phase-matched parametric processes
in KTP demonstrates evident advantages in comparison with that of widely used MgO-doped
LiNbO3 crystals.

Keywords: KTP; nonlinear crystal; frequency conversion; SHG; DFG; THz radiation; THz wave

1. Introduction
Potassium titanyl phosphate (KTiOPO4 , KTP) is one of the most widely used nonlinear optical
crystals [1]. KTP belongs to the mm2 point group symmetry and its dielectric and crystallographic axes
are assigned as X, Y, Z → a, b, c. Its structure consists of chains of connected rigid PO4 tetrahedra
and TiO6 octahedra with alternating long and short Ti–O bonds that are responsible for its nonlinear
properties [2]. KTP advantages are high nonlinear coefficients: d15 = 1.9 pm/V, d24 = 4.2 pm/V,
d31 = 2.2 pm/V, d32 = 2.7 pm/V and d33 = 17.4 pm/V, wide ranges of angles and temperatures for the
phase matching, low absorption in the range of 0.35 µm to 4.5 µm, excellent mechanical stability and
optical quality. One of the few KTP disadvantages is its susceptibility to photochromic damage, that is,
grey-tracking, that causes slow deterioration of light conversion efficiency.
The abovementioned properties of KTP determine its wide range of nonlinear applications such
as sum [3] and difference [4,5] frequency generation (SFG and DFG), second harmonic generation
(SHG) [6], optical parametric oscillation/generation (OPO/OPG) and amplification (OPA) [7–9].
Parametric generation based on stimulated polariton scattering in KTP shows superior performance in
terms of gain and laser damage resistance in comparison to lithium niobate and lithium tantalate [10,11].
Other KTP applications include modulators for the near- and the mid-IR ranges [12–14].

Crystals 2018, 8, 310; doi:10.3390/cryst8080310 www.mdpi.com/journal/crystals

Crystals 2018, 8, 310 2 of 8
Crystals 2018, 8, x FOR PEER REVIEW 2 of 8

The success
successofofKTP KTP nonlinear
nonlinear applications
applicationsin the
in visible and IRand
the visible ranges
IR drives
rangesinterest
drives in studying
interest in
its terahertz
studying its dielectric
terahertz and opticaland
dielectric (THz) properties
optical (THz) to substitutetothe
properties widely used
substitute pure and
the widely MgO-doped
used pure and
lithium
MgO-doped niobate crystals
lithium (LiNbO
niobate 3 , LN)
crystals in this
(LiNbO range
3, LN) in[15]. Previously,
this range infrared reflectivity
[15]. Previously, spectrum
infrared reflectivity
spectrum
of KTP was of studied
KTP wasup studied up to the wavenumber
to the wavenumber of 4000 cm of−4000
1 (120cm −1 (120
THz) at THz) at the temperatures
the temperatures of 7 K, 80 of K
7
K, 80 K and 293 K [16]. Later, the results were supplemented by Raman spectroscopy measurements
and 293 K [16]. Later, the results were supplemented by Raman spectroscopy measurements at the
at the wavenumbers
wavenumbers below below
4000 cm −1 [17].
4000 cm−1 Recently,
[17]. Recently, THz refractive
THz refractive indexindex and absorption
and absorption coefficient
coefficient were
were directly
directly measured
measured usingusing growingly
growingly accessible
accessible THzTHz time-domain
time-domain spectrometers
spectrometers (THz-TDS)
(THz-TDS) [18–
[18–21].
21]. The
The mostmost comprehensive
comprehensive studystudy
of itsofTHz
its THz optical
optical properties
properties for the
for the waves
waves polarized
polarized parallel
parallel to
to all
all three
three optical
optical axesaxes of KTP
of the the KTP crystals
crystals was was carried
carried out inout in [20].
[20]. The refractive
The refractive indexindex components
components at room at
room temperature
temperature were approximated
were approximated in the informtheof
form of Sellmeier
Sellmeier equations
equations [21]. [21].
In this paper, we report terahertz optical properties of KTP crystals at the room temperature of
(RT) and
293 K (RT) andatatthe
theliquid
liquidnitrogen
nitrogentemperature
temperature ofof
8181 K and
K and calculate
calculate phase-matching
phase-matching conditions
conditions for
for nonlinear
nonlinear frequency
frequency conversion
conversion intointo
andand within
within the the
THzTHz range.
range.

2. Materials and
2. Materials and Methods
Methods
KTP
KTP single-crystal
single-crystalingots
ingotswereweregrown
grownusing
usingthethe
Czochralski
Czochralski method
method from a Ptacrucible
from of 100
Pt crucible of mm
100
in
mm diameter.
in diameter.The crucible closedclosed
The crucible with Ptwith
coverPtwith
coverabout
with1 about
kg of charge
1 kg ofwas disposed
charge was in the resistivity
disposed in the
oven. Afteroven.
resistivity heating,
Aftertheheating,
melt was thehomogenized and cooled down
melt was homogenized to liquidus
and cooled downtemperature. The crystals
to liquidus temperature.
were grown using single-domain seed in the direction of X-axis.
The crystals were grown using single-domain seed in the direction of X-axis. During the During the growth period
growth of
45–55 ◦ ◦
perioddays, the melt
of 45–55 days,was
thecooled
melt wasdown by 70–120
cooled down C. byThe cooling
70–120 °С. rate
The of the crystal
cooling was
rate of the0.1–4
crystal C/day
was
while its rotation speed varied from 30 to 40 rpm. In parallel, the pulling
0.1–4 °С/day while its rotation speed varied from 30 to 40 rpm. In parallel, the pulling speed speed changed from 0 to
1.2 mm/day. By selecting optimal growth conditions high-quality single-crystal
changed from 0 to 1.2 mm/day. By selecting optimal growth conditions high-quality single-crystal ingots having a weight
of 260 ghaving
and dimensions X× Y × dimensions
Z = 40 × 60 of ×X 3
ingots a weight ofof260 g and 70×mmY × Zwere
= 40 grown.
× 60 × 70 mm3 were grown.
3 was manufactured
At first, a large plate with dimensions of X × Y × Z = 11 × 2828× ×
At first, a large plate with dimensions of X × Y × Z = 11 × 58 58
mmmm3 was manufactured to
to evaluate
evaluate thethe quality
quality of of
thethegrown
growncrystal
crystaland
andmeasure
measureits its transmission
transmission spectrum
spectrum in in the
the main
main
transparency
transparency window.window.Then Then three
three pairs
pairs samples
samples withwith different
different thickness
thickness with dimensions
with dimensions of 10 × 10of
10 × 10 × (0.28, 0.35 and 1.08) mm 3 were cut orthogonal to the optical axes X (KTP ) and Z (KTP )
× (0.28, 0.35 and 1.08) mm were cut orthogonal to the optical axes X (KTPx) and Z (KTP
3 x z) (Figure 1). z
(Figure
Sides of1). theSides
KTPof the KTPwere
x sample x sample wereto
parallel parallel
the Y to theZYaxes
and Z axes
and and andof
sides sides
the of thez KTP
KTP samplez sample
were
were parallel
parallel to thetoXthe X and
and Y axes.
Y axes. So, every
So, every pairpair of samples
of samples allowed
allowed ususto to measureallallthree
measure three(x,(x,yyand
and z)z)
components of the absorption coefficient and refractive index for waves polarized
components of the absorption coefficient and refractive index for waves polarized parallel to the X, Y parallel to the X, Y
and Z
and Z axes,
axes, respectively
respectively andand select
select the
the best-thickness
best-thickness crystals
crystals for
for the
the study.
study.

Figure 1. A pair of prepared KTP crystal samples cut orthogonal to the X and Z axes.
Figure 1. A pair of prepared KTP crystal samples cut orthogonal to the X and Z axes.

Transmission spectra in the transparency window were measured by UV-2101/3101

Transmission spectra in the transparency window were measured by UV-2101/3101
spectrophotometer (Shimadzu, Kyoto, Japan). Terahertz optical properties were studied using a
spectrophotometer (Shimadzu, Kyoto, Japan). Terahertz optical properties were studied using
THz-TDS (IA&E SB RAS, Novosibirsk, Russia) with a cryostat described elsewhere [20] at the
temperatures of 293 K and 81 K.
Crystals 2018, 8, 310 3 of 8

a THz-TDS (IA&E SB RAS, Novosibirsk, Russia) with a cryostat described elsewhere [20] at the
Crystals 2018, 8, xof
temperatures FOR
293PEER REVIEW
K and 81 K. 3 of 8

3. Results
3.
The resistivity
The resistivity of of aa grown
grown KTP KTP crystal
crystal isis one
one of
of indicators
indicators of of its
its quality.
quality. Higher
Higher values
values ofof
resistivity make
resistivity makethe thecrystals
crystals applicable
applicable for manufacturing
for manufacturing electro-optic
electro-optic devices:
devices: amplitude
amplitude and
and phase
phase modulators
modulators [12]. 2a
[12]. Figure Figure 2a depicts
depicts crystal resistivity
crystal resistivity which
which stays stays
larger larger
than Ω cm
1011than 10for
11 Ωthe
cmapplied
for the
appliedfield
electric electric field
up to up to 20proving
20 kV/cm kV/cm proving highand
high quality quality
easyand easy polarizability
polarizability of the for
of the samples samples for
creating
creating periodical structures. Visible and IR range transmission spectrum
periodical structures. Visible and IR range transmission spectrum of thick KTP plate for the waveof thick KTP plate for the
wave propagating
propagating along along
X axisXand axispolarized
and polarized parallel
parallel to Z to Z axis
axis is presented
is presented in Figure
in Figure 2a. 2a.
TheThe quality
quality of
of the
the grown
grown crystals
crystals is additionally
is additionally supported
supported by the
by the lacklack
of aof a wide
wide absorption
absorption bandband around
around 28002800
nm
nm is
that that is attributed
attributed to O–Htobonds.O–H Thebonds. The measured
measured transmission transmission
corresponds corresponds
to absorption to coefficients
absorption
below 10−3 cm
coefficients −1 . Thus,
below 10−3 cmKTP−1. Thus,
crystalsKTP
cancrystals
be pumped can in
bethe
pumped
range ofin 0.375–4.2
the rangeµm of by
0.375–4.2 µm IR
visible and by
visible and
radiation IR radiation
including including
chemical chemical
lasers. The absence lasers. The absence
of two-photon of two-photon
absorption absorption
while pumping while
by widely
pumping
used by widelylasers
all-solid-state used such
all-solid-state lasers (0.8–1.1
as Ti:Sapphire such as µm),
Ti:Sapphire
Nd:YAG (0.8–1.1
(1.064µm),
µm),Nd:YAG
holmium(1.064
(2.01 µm),
holmium
erbium (2.01
(2.94 µm),
µm) Fe2+ :ZnSe
anderbium (2.94(4.1
µm) andisFe
µm) 2+:ZnSe (4.1
attractive µm) is attractive
for applied systems. for applied systems.

(a) (b)
Figure 2.
Figure 2. (a)
(a) A
A typical
typical dependence
dependence of
of resistivity
resistivity on
on the
the applied
applied electric
electric field
field of
of the
the grown
grown KTP
KTP ingot;
ingot;
(b) Transmission spectra of thick KTP plate for radiation polarized parallel to Z axis in the visible
(b) Transmission spectra of thick KTP plate for radiation polarized parallel to Z axis in the visible and and
IR ranges.
IR ranges.

Absorption of the KTP crystal recorded by THz-TDS decreases at higher wavelengths (Figure
Absorption of the KTP crystal recorded by THz-TDS decreases at higher wavelengths (Figure 3).
3). This behaviour arises from the presence of several phonon modes below 200 µm. X and Y axes
This behaviour arises from the presence −1 of several phonon modes below 200 µm. X and Y axes
demonstrate the lowest absorption (<5 cm−1 for wavelengths >360 µm) especially after cooling down
demonstrate the−1lowest absorption (<5 cm for wavelengths >360 µm) especially after cooling down
to 81 K (<1 cm for wavelengths >250 µm). The measured absorption coefficient of KTP crystal is
to 81 K (<1 cm−1 for wavelengths >250 µm). The measured absorption coefficient of KTP crystal is
significantly lower compared to 0.7% MgO-doped stoichiometric lithium niobate which is preferable
significantly lower compared to 0.7% MgO-doped stoichiometric lithium niobate which is preferable
for terahertz wave generation (see Figure 3a for comparison) [22,23]. The wavelengths above 500 µm
for terahertz wave generation (see Figure 3a for comparison) [22,23]. The wavelengths above 500 µm
are also free from strong water vapour absorption lines and are of interest for gas analysis with THz
are also free from strong water vapour absorption lines and are of interest for gas analysis with
lidar.
THz lidar.

(a) (b)
Figure 3. Measured absorption coefficient of KTP compared to 0.7% MgO-doped stoichiometric
lithium niobate (LN, adapted from [23]) at: (a) Room temperature; (b) Liquid nitrogen temperature.
3). This behaviour arises from the presence of several phonon modes below 200 µm. X and Y axes
demonstrate the lowest absorption (<5 cm−1 for wavelengths >360 µm) especially after cooling down
to 81 K (<1 cm−1 for wavelengths >250 µm). The measured absorption coefficient of KTP crystal is
significantly lower compared to 0.7% MgO-doped stoichiometric lithium niobate which is preferable
for terahertz wave generation (see Figure 3a for comparison) [22,23]. The wavelengths above 500 µm
Crystals 2018, 8, 310 4 of 8
are also free from strong water vapour absorption lines and are of interest for gas analysis with THz
lidar.

(a) (b)
Figure 3. Measured absorption coefficient of KTP compared to 0.7% MgO-doped stoichiometric
Figure 3. Measured absorption coefficient of KTP compared to 0.7% MgO-doped stoichiometric lithium
lithium (LN,
niobate niobate (LN, adapted
adapted from
from [23]) [23])
at: (a) at: (a)
Room Room temperature;
temperature; (b)nitrogen
(b) Liquid Liquid nitrogen temperature.
temperature.
Crystals 2018, 8, x FOR PEER REVIEW 4 of 8

Refractive index components for the long-wavelength terahertz range measured by TH-TDS at
temperatures are
the room and liquid nitrogen temperatures are shown
shown in
in Figure
Figure 4a,b,
4a,b, respectively.
respectively.

(a) (b)
Figure 4. Measured (circles) and approximated (sold lines) dispersion of refractive index
Figure 4. Measured (circles) and approximated (sold lines) dispersion of refractive index components
components of KTP at: (a) Room temperature; (b) Liquid nitrogen temperature.
of KTP at: (a) Room temperature; (b) Liquid nitrogen temperature.

Recorded dispersions were approximated in the form of Sellmeier equations by the best-fit
Recorded
method withindispersions
the spectralwere approximated
range of 142 µm toin1500 the form
µm atofthe
Sellmeier equations by[21]:
room temperature the best-fit method
within the spectral range of 142 µm to 1500 µm at the room temperature [21]:
1.14398λ
2
2
nx = 9.54967 +1.14398λ , 2
n2x = 9.54967 + λ2 2 − 13637 ,
λ − 13637
22
n2y n=2 =9.72515 + 1.26864λ ,
1.26864λ
(1)
y
9.72515 +λ2 2− 13889 , (0)
λ − 13889
2.29045λ2
n2z = 13.4416 + 2 .
λ
2
2
− 11799
λ2.29045
nz = 13.4416 + 2 .
λ − 11799
Corresponding Sellmeier equations for 81 K could be written as follows:

1.20539λ
2
2
nx = 9.07963 + ,
λ − 12497
2

1.36025λ
2
2
n y = 9.20704 + , (0)
λ − 12264
2

2.36823λ
2
2
nz = 11.8979 + .
λ − 11336
2
 Crystals 2018, 8, 310 5 of 8

Corresponding Sellmeier equations for 81 K could be written as follows:

1.20539λ2
n2x = 9.07963 + ,
λ2 − 12497
1.36025λ2
n2y = 9.20704 + 2 , (2)
λ − 12264
2.36823λ2
n2z = 11.8979 + 2 .
λ − 11336

Approximation curves calculated using sets of Equations (1) and (2) are also depicted in Figure 4.
It should be emphasized that the KTP refraction index is much smaller than that of LiNbO3 crystals
(~5.2) [22] and collinear velocity-matching appears to be possible in contrast to LN crystal.
By using known dispersion equations for the refractive index for the main transparency window
and its temperature dependence [1] and Equations (1) and (2), the dependence of V z angle versus
Crystals 2018, 8, xisFOR
wavelength PEER REVIEW
calculated for the entire transparency range of KTP (Figure 5). 5 of 8

Figure 5. Spectral dependence of the Vz angle in the principle XZ plane at RT and 81 K.

Figure 5. Spectral dependence of the V z angle in the principle XZ plane at RT and 81 K.

Figure 5 shows that Vz angle is weakly dependent on the crystal temperature, that is,
Figure 5 shows
phase-matching should that
be alsoV zinsensitive
angle is to weakly dependentvariations
the temperature on the crystal temperature,
in contrast that Itis,
to LiNbO3 [15].
phase-matching should be also insensitive to the temperature variations in
is interesting to note that Vz position in the long wavelength region of the THz range is not contrast to LiNbO 3 [15]. It is
interesting to note that
dependent on the wavelength, V z position in the long wavelength region of the THz range
that is, effective nonlinearity is not dependent on the pump is not dependent on
the wavelength,
wavelength that is, effective
for frequency nonlinearity
conversion processes is within
not dependent
it. on the pump wavelength for frequency
conversion processes within it.
Phase matching for difference frequency generation into the THz range under visible and
near-IRPhase
pump matching
is foundforpossible
differenceonlyfrequency generation
in the principle XZinto the(at
plane THzθ >range
Vz and under
θ < Vvisible and near-IR
z) at RT and 81 K
pump is found possible only in the principle XZ plane (at θ > V and < V ) at
by s − f → f and s − f → s types of interactions. Here, s and f symbols denote slow and fast interacting
z θ z RT and 81 K by s − f
→ f and s − f → s types of interactions. Here, s and f symbols denote slow
waves, respectively. For example, phase-matching curves for frequency conversion of tunable and fast interacting waves,
respectively.
(0.65–1.1 For example,
µm) Ti:Sapphire phase-matching
laser are presentedcurves for frequency
in Figure 6. conversion of tunable (0.65–1.1 µm)
Ti:Sapphire laser are presented in Figure 6.
It is seen in Figure 6 that type I and type II interactions have very close phase-matching conditions.
For interactions in the XZ plane, when Kleinman symmetry conditions are not valid, effective nonlinear
coefficient is ds −f→f = d32 ·sinθ for θ < V z and ds −f→s = d24 ·sinθ for θ > V z [1]. At 1.064 µm d24 ≈ d32 =
3.7 pm/V. So, DFG at larger angles is preferable for both processes due to higher nonlinear coefficient
and smaller absorption. Group velocity matching at θ > V z is better for the shortest pump wavelength.
Thus, ultrashort pulse conversion can be more efficient, for example, under the pump of THL-100
hybrid laser system built in the Institute of High Current Electronics, Siberian Branch of Russian
 phase-matching should be also insensitive to the temperature variations in contrast to LiNbO3 [15]. It
is interesting to note that Vz position in the long wavelength region of the THz range is not
dependent on the wavelength, that is, effective nonlinearity is not dependent on the pump
wavelength for frequency conversion processes within it.
Phase matching for difference frequency generation into the THz range under visible and
Crystals 2018, 8, 310 6 of 8
near-IR pump is found possible only in the principle XZ plane (at θ > Vz and θ < Vz) at RT and 81 K
by s − f → f and s − f → s types of interactions. Here, s and f symbols denote slow and fast interacting
Academyrespectively.
waves, of Sciences: λFor example,
= 475 phase-matching
nm (wavelength), τ = 50 curves
fs (pulsefor frequency
duration), conversion
d = 25 cm (pulseof tunable
aperture),
P(0.65–1.1
= 14 TWµm) Ti:Sapphire
(pulse laser
power) and E =are
1 Jpresented in Figure
(pulse energy) [24].6.

Crystals 2018, 8, x FOR PEER REVIEW 6 of 8

(a) (b)
shortest pump
Figure wavelength. Thus, ultrashort (a)spulse →conversion − can
ff → be more efficient, for example,
Figure 6.6.Phase-matching
Phase-matching curvesfor
curves forDFG
DFG(a) s−−ff → ff and
and (b)
(b) ss − → ss types of Ti:Sapphire
types of Ti:Sapphire laser
laser (at
(at
under the
0.65, pump
0.8 and of
1.1THL-100
µm): hybrid
optical laser system
rectification or built
mixing in
of the
two Institute
close of High
wavelength Current
lasers
0.65, 0.8 and 1.1 µm): optical rectification or mixing of two close wavelength lasers in the XZ principle in Electronics,
the XZ
Siberian
plane Branch
principle plane
of KTP ofofRussian
KTP
crystal Academy
crystal
at RT atlines)
(solid of 81
RT (solid
and Sciences:
lines) and 81
K (dashed λK =(dashed
475versus
lines) nm θ(wavelength),
lines) versus θ angle.
angle. τ = 50 fs (pulse
duration), d = 25 cm (pulse aperture), P = 14 TW (pulse power) and E = 1 J (pulse energy) [24].
It is
By seenrelations
using in Figure 6 that
(1) and (2),type
phase I and type for
matching II interactions
collinear second haveharmonic
very close phase-matching
generation of THz
By using relations (1) and (2), phase matching for collinear second harmonic generation of THz
conditions.
waves is alsoFor interactions
found possible in
by the
typeXZ + s → when
I (splane, f) and Kleinman s → f) of three-wave
type II (f + symmetry conditionsinteractions
are not valid, in
waves is also found possible by type I (s + s → f ) and type II (f + s → f ) of three-wave interactions in
effective
the nonlinear
XZ plane. Figurecoefficient
7 plots theisphase-matching
ds−f→f = d32·sinθ for θ < Vfor
curves z and
type ds−fII→SHG.
s = d24·Phase-matching
sinθ for θ > Vz [1]. At 1.064
conditions
the XZ plane. Figure 7 plots the phase-matching curves for type II SHG. Phase-matching conditions
µmtype
for d24 ≈ Id32
and= 3.7
type pm/V.
II SHGSo, of
DFG at larger
longer THz angles
waves isare preferable
found close for both processes
to each other, due
that tois,higher
their
for type I and type II SHG of longer THz waves are found close to each other, that is, their efficiencies
nonlinear coefficient
efficiencies also shouldand smaller
be close. absorption.
Cooling down Group velocity
KTP crystal to 81matching
K resultsat inθ◦a small
> Vz is(1°)
better for the
increase of
also should be close. Cooling down KTP crystal to 81 K results in a small (1 ) increase of V z angle
Vz angle (Figure 5) but it provides with efficient control of group velocity matching conditions.
(Figure 5) but it provides with efficient control of group velocity matching conditions.

Figure 7. Phase-matching
Phase-matching curves
curves for SHG of THz waves by f + + s → f type
type of interaction
interaction in the XZ
principle plane of KTP versus θθ and
and ϕφangles
anglesthat
thatisisidentified
identifiedin
inthe
thefigure
figureinset.
inset.

4. Discussion
4. Discussion
canbe
It can beproposed
proposed that
that minimal
minimal absorption
absorption coefficient
coefficient of crystal
of KTP KTP crystal is determined
is determined by the
by the residual
residual structure
domain domain structure that
that can be can be by
decreased decreased by application
application of higher
of higher voltage voltage optimization
and further and further
optimization
of the growthof the growth
process. process.
Further Further
cooling belowcooling
81 K canbelow 81 K
narrow thecan narrow
phonon theand
lines phonon linestheir
decrease and
decrease their wavelength extending the THz transparency range toward shorter wavelengths.
Furthermore, cooling can increase the damage threshold leading to improved frequency conversion
efficiency that is a subject of future study. THz wave energy can be seriously scaled up by using
large aperture KTP samples pumped by ultrashort pulse terawatt (TW) laser systems that should be
studied experimentally.
Crystals 2018, 8, 310 7 of 8

wavelength extending the THz transparency range toward shorter wavelengths. Furthermore, cooling
can increase the damage threshold leading to improved frequency conversion efficiency that is a subject
of future study. THz wave energy can be seriously scaled up by using large aperture KTP samples
pumped by ultrashort pulse terawatt (TW) laser systems that should be studied experimentally.
Finally, low absorption at visible-IR pump wavelengths and long THz wavelengths (≥500 µm at
RT and 125 µm at 81 K) together with the exceptional set of known physical properties render KTP
crystal amongst the most prospective ones for long wavelength THz generation by phase-matched
parametric processes. It demonstrates evident advantages in comparison with widely used MgO-doped
LiNbO3 crystals. Available growth technology for producing large-size KTP crystals and TW-level
pump systems can allow generation of high-power ps-scale THz pulses.

Author Contributions: Conceptualization, Y.A.; Methodology, A.M. (Arkady Meshalkin) and V.A.; Software, A.M.
(Alexander Mamrashev) and G.L.; Formal Analysis, A.M. (Alexander Mamrashev), N.N. and G.L.; Investigation,
N.N. and A.M. (Arkady Meshalkin); Data Curation, A.M. (Alexander Mamrashev), N.N., G.L.; Writing-Original
Draft Preparation, Y.A.; Writing-Review & Editing, A.M. (Alexander Mamrashev), N.N. and Y.A.; Visualization,
G.L.; Supervision, Y.A. and V.A.
Funding: This research was funded by Russian Foundation for Basic Research (RFBR) grant number 17-32-80039
and complex program of basic academic research of Russian Ministry of Science and Higher Education (State
Registration No. AAAA-A17-117052410033-9).
Acknowledgments: The terahertz spectroscopy measurements were carried out on the time-domain terahertz
spectrometer at the Shared Equipment Center “Spectroscopy and Optics” of the Institute of Automation and
Electrometry SB RAS, Novosibirsk, Russia.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Nikogosyan, D. Nonlinear Optical Crystals: A Complete Survey; Springer: New York, NY, USA, 2005;
ISBN 978-0-387-22022-2.
2. Sorokina, N.I.; Voronkova, V.I. Structure and properties of crystals in the potassium titanyl phosphate family:
A review. Crystallogr. Rep. 2007, 52, 80–93. [CrossRef]
3. Haiyong, Z.; Ge, Z.; Chenghui, H.; Yong, W.; Lingxiong, H.; Zhenqiang, C. Multi-watt power blue light
generation by intracavity sum-frequency-mixing in KTiOPO4 crystal. Opt. Express 2008, 16, 2989–2994.
[CrossRef] [PubMed]
4. Bhar, G.C.; Rudra, A.M.; Chaudhary, A.K.; Sasaki, T.; Mori, Y. Highly efficient difference-frequency generation
in KTP. Appl. Phys. B Laser Opt. 1996, 63, 141–144. [CrossRef]
5. Bhar, G.C.; Chatterjee, U.; Rudra, A.M.; Chaudhary, A.K. Generation of widely tunable mid-infrared radiation
by difference frequency mixing in KTP. J. Phys. D Appl. Phys. 1997, 30, 2693–2697. [CrossRef]
6. Zheng, J.; Zhao, S.; Wang, Q.; Zhang, X.; Chen, L. Influence of thermal effect on KTP type-II phase-matching
second-harmonic generation. Opt. Commun. 2001, 199, 207–214. [CrossRef]
7. Colville, F.G.; Dunn, M.H.; Ebrahimzadeh, M. Continuous-wave, singly resonant, intracavity parametric
oscillator. Opt. Lett. 1997, 22, 75–77. [CrossRef] [PubMed]
8. Isaienko, O.; Borguet, E. Generation of ultra-broadband pulses in the near-IR by non-collinear optical
parametric amplification in potassium titanyl phosphate. Opt. Express 2008, 16, 3949–3954. [CrossRef]
[PubMed]
9. Tang, M.; Minamide, H.; Wang, Y.; Notake, T.; Ohno, S.; Ito, H. Dual-wavelength single-crystal double-pass
KTP optical parametric oscillator and its application in terahertz wave generation. Opt. Lett. 2010, 35,
1698–1700. [CrossRef] [PubMed]
10. Wang, W.; Cong, Z.; Chen, X.; Zhang, X.; Qin, Z.; Tang, G.; Li, N.; Wang, C.; Lu, Q. Terahertz parametric
oscillator based on KTiOPO4 crystal. Opt. Lett. 2014, 39, 3706–3709. [CrossRef] [PubMed]
11. Wu, M.-H.; Chiu, Y.-C.; Wang, T.-D.; Zhao, G.; Zukauskas, A.; Laurell, F.; Huang, Y.-C. Terahertz parametric
generation and amplification from potassium titanyl phosphate in comparison with lithium niobate and
lithium tantalate. Opt. Express 2016, 24, 25964–25973. [CrossRef] [PubMed]
12. Rusov, V.A.; Serebryakov, V.A.; Kaplun, A.B.; Gorchakov, A.V. Using modulators based on KTP crystals in
Nd: YAG lasers with high mean power. J. Opt. Technol. 2009, 76, 325–331. [CrossRef]
Crystals 2018, 8, 310 8 of 8

13. Rusov, V.A.; Zakharova, N.A.; Kaplun, A.B.; Meshalkin, A.B.; Gorshakov, A.V. Study of the
electrical-conductivity kinetics of KTP crystals used in the modulators of solid-state lasers. J. Opt. Technol.
2013, 80, 532–536. [CrossRef]
14. Rusov, V.A.; Serebryakov, V.A.; Doroganov, S.V.; Kalintseva, N.A.; Narivonchik, A.S.; Skvortsov, D.V.
Electro-optical modulators based on KTP crystals for high-power lasers in the mid-IR region. J. Opt. Technol.
2016, 83, 716–721. [CrossRef]
15. Stepanov, A.G.; Henin, S.; Petit, Y.; Bonacina, L.; Kasparian, J.; Wolf, J.-P. Mobile source of high-energy
single-cycle terahertz pulses. Appl. Phys. B 2010, 101, 11–14. [CrossRef]
16. Wyncke, B.; Brehat, F.; Mangin, J.; Marnier, G.; Ravet, M.F.; Metzger, M. Infrared reflectivity spectrum of
KTiOPO4 single crystal. Phase Transit. 1987, 9, 179–183. [CrossRef]
17. Kugel, G.E.; Brehat, F.; Wyncke, B.; Fontana, M.D.; Marnier, G.; Carabatos-Nedelec, C.; Mangin, J.
The vibrational spectrum of a KTiOPO4 single crystal studied by Raman and infrared reflectivity spectroscopy.
J. Phys. C Solid State Phys. 1988, 21, 5565. [CrossRef]
18. Mounaix, P.; Sarger, L.; Caumes, J.P.; Freysz, E. Characterization of non-linear potassium crystals in the
terahertz frequency domain. Opt. Commun. 2004, 242, 631–639. [CrossRef]
19. Sang, M.; Fan, L.; Lu, X.; Zhang, W. Optical phonon resonance of KTiOPO4 crystal characterized by THz
time-domain spectroscopy. Acta Photonica Sin. 2009, 32, 1286–1290.
20. Antsygin, V.D.; Kaplun, A.B.; Mamrashev, A.A.; Nikolaev, N.A.; Potaturkin, O.I. Terahertz optical properties
of potassium titanyl phosphate crystals. Opt. Express 2014, 22, 25436–25443. [CrossRef] [PubMed]
21. Huang, J.-G.; Huang, Z.-M.; Nikolaev, N.A.; Mamrashev, A.A.; Antsygin, V.D.; Potaturkin, O.I.;
Meshalkin, A.B.; Kaplun, A.B.; Lanskii, G.V.; Andreev, Y.M.; et al. Phase matching in RT KTP crystal
for down-conversion into the THz range. Laser Phys. Lett. 2018, 15, 075401. [CrossRef]
22. Yeh, K.-L.; Hoffmann, M.C.; Hebling, J.; Nelson, K.A. Generation of 10 µJ ultrashort terahertz pulses by
optical rectification. Appl. Phys. Lett. 2007, 90, 171121. [CrossRef]
23. Unferdorben, M.; Szaller, Z.; Hajdara, I.; Hebling, J.; Pálfalvi, L. Measurement of refractive index and
absorption coefficient of congruent and stoichiometric lithium niobate in the terahertz range. J. Infrared
Millim. Terahertz Waves 2015, 36, 1203–1209. [CrossRef]
24. Alekseev, S.V.; Ivanov, M.V.; Ivanov, N.G.; Losev, V.F.; Mesyats, G.A.; Panchenko, Y.N.; Ratakhin, N.A.
Parameters of the THL-100 hybrid femtosecond laser system after modernization. Russ. Phys. J. 2015, 58,
1087–1092. [CrossRef]

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).