Borate Materials in Nonlinear Optics

By Petra Becker*
1. Introduction
In 1961, shortly after the demonstration of the first laser, Franken et al.[1] observed second harmonic generation (SHG) for the first time by propagating a ruby laser beam through a quartz crystal. Since then, very intensive research has been carried out in the field of nonlinear optical (NLO) devices, as they are capable of expanding the frequency range provided by common laser sources. Nowadays they are widely used, for example, in laser medicine, optical communication and signal processing, and more and more in the expanding field of integrated optics. Especially the latter two topics require laser beam sources in the UV region, for example, to enhance the possible information storage density on compact discs. Furthermore, optical parametric processes are able to produce tunable laser radiation from UV to the near IR. This increase in the number of frequencies available for use with optical fibers increases the information carrying capability of such systems. Another interesting application to basic materials research is the upconversion of ultrashort laser pulses (~10 fs) from red (Ti:sapphire) to blue[2] to extend the possibilities of spectroscopic studies of ultrafast phenomena, for example, carrier relaxation dynamics in semiconducting materials, to IIVI semiconductors (with a bandgap in the blue spectral region, e.g., ZnSe), which are very promising materials for the realization of blue lightemitting diodes (LEDs). In these fields, great progress has been made since the advent of the first high-tech borate material b-BaB2O4 about 15 years ago[3,4] and the subsequent discovery of several further suitable borate compounds. Borates are superior in UV applications to other commonly used NLO materials such as potassium dihydrogen phosphate (KDP) or LiNbO3 because of their high UV transmittance at wavelengths down to 155 nm[15,16] combined with a high damage threshold. A comparison of selected NLO materials is given in Table 1. In this review a summary of the main properties that determine an effective NLO material is given for recently described borate compounds that are used or intended for NLO applications.
Table 1. Comparison of the damage threshold and the optical transmittance range of selected nonlinear optical materials.

[a] At l = 1064 nm and tp = 10 ns.

2. Basic Principles
In the following some basic principles of nonlinear optics will be discussed very briefly. For a more comprehensive treatise, the reader is referred to other literature on nonlinear optics.[2024] A general introduction to (linear) crystal optics can be found in standard textbooks.[2527] The origin of NLO processes is the response of a nonlinear dielectric medium to an oscillating electric field. For an applied low amplitude oscillating field on the crystal structure and its electron distribution the induced oscillation of charges in the structure results in the radiation of an electromagnetic field with a frequency equal to the applied field oscillation. If, however, a harmonic oscillation with a sufficiently high amplitude is applied, then radiation that is described by a combination of the induced frequency and its harmonics is produced. Therefore, NLO processes in optical media, caused by intense electromagnetic radiation fields, generate new frequencies of light. With respect to the electromagnetic field the processes can either be energy conserving such as harmonic generation or energy consuming such as stimulated Raman or Brillouin scattering. In harmonic generation, a single harmonic (frequency doubling, tripling, etc.) of a given fundamental frequency is generated by the nonlinear response of the material. The induced dielectric polarization P depends on the applied field E and can be expressed in a series of powers of E, according to Equation 1, where w(1) is the linear dielectric susceptibility known from linear optics, and w(2), w(3), etc. are the nonlinear dielectric susceptibilities of second, third, etc. order, respectively. P(E) = e0(w(1)E + w(2)E2 + w(3)E3 + _) (1)

[*] Dr. P. Becker Institut fr Kristallographie der Universitt zu Kln Universitt Kln Zlpicher Strasse 49b, D-50674 Kln (Germany)

Unfortunately, not all materials are suitable for NLO applications. Nonlinear second-order susceptibility only
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occurs in crystals without a center of symmetry, in centric crystals it is zero. Table 2 gives a representative summary of important NLO processes together with their relevant terms of w(n). In the case of SHG (o1 = o2, o3 = 2o1) a SHG tensor dijk is commonly used in the literature, which is defined as dijk = wijk/2. It should be noted that the generation of the third harmonic reported in the literature is usually achieved by sum frequency generation of the fundamental frequency and its second harmonic by o3 = o1 + 2o1 because it has a much higher efficiency than the third-order process. In general, parametric processes such as SHG are seldom efficient unless a degree of index matching between the frequencies present is possible. This means that, for reasons of energy conservation, for wavevectors ki (i = 1,2,3,4), corresponding to the waves with frequencies oi, the phasematching conditions shown in Equation 2 have to be fulfilled, where the quantities n(oi) and u(oi) are the refractive index and the phase velocity at the frequency oi, respectively. In practice, this means, for example, for SHG and scalar phase matching (o1 = o2, o3 = 2o1) that k3 = 2k1 or n3 = n1.

k3 = k2 + k1 or k4 = k2 k1 where jki j

oi noi oi (2) c uoi

Due to normal dispersion of transparent isotropic materials (n1 < n3) this condition can never be fulfilled. In practice, however, the problem can be by-passed either by use of an anomalous dispersion (but this works only for very special frequencies and is therefore only rarely used) or by using the natural birefringence of uniaxial or biaxial crystals.[28,29] By an appropriate choice of polarization and direction of propagation of light through the crystal it is often possible to fulfill the phase-matching conditions. Figure 1 depicts the principles of phase matching of a uniaxial negative crystal as an example. Readers who are interested in a more detailed and systematic discussion of phase matching for uniaxial and biaxial crystals are referred to the paper by Hobden.[30]

3. Borate Materials
NLO materials are materials used to generate new laser sources of frequencies that cannot be obtained directly

Table 2. Representative summary of nonlinear optical processes and the frequency arguments of w(n).

[a] Subscripts: s = Stokes, p = pump.

Petra Becker studied mineralogy at the University of Stuttgart, completing her Masters at the Institute for Theoretical and Applied Physics. In 1992 she gained her Ph.D. for work on the crystal growth and characterization of acentric borate materials from Ludwig-MaximiliansUniversitt, Munich. At present she is an assistant lecturer at the Institute for Crystallography at Cologne University, where her interests are focused on the crystal chemistry and crystal growth of borate materials for nonlinear optical applications. 980
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Fig. 1. Cross section of the index surface of a uniaxial negative crystal with indicated phase-matching angles yI and yII for type I and type II phase m m matching. Solid line: index surface for the fundamental wave with frequency o. Dashed: index surface for the second harmonic with frequency 2o. Dotted: surface (no + no)/2. e and o are abbreviations for extraordinary wave o e and ordinary wave, respectively.

from available lasers. In the narrow sense applied here NLO materials are used for sum frequency generation processes described by second-order nonlinear susceptibility, w(2). Efficient frequency conversion is not only dependent on the field strength and frequencies of the incident beams but also on crystal properties such as the effective nonlinear coefficient, refractive indices, phase-matching conditions, and damage threshold. As a general rule, the basic conditions apart from the non-centrosymmetry of the crystal structure are: 1) relatively large dijk coefficients, 2) moderate birefringence, 3) wide transparency range (either in IR or UV), 4) wide phase-matching range, 5) high damage threshold, 6) good chemical and mechanical stability, and 7) ease to grow. No crystal material can meet all the above conditions simultaneously because optimization of one property, for example, (1), causes a deterioration of another, which is related through physics to, for example, (2). But since the different optical frequencies in use require different properties of NLO materials, the efforts in materials research nowadays are tending toward a materials engineering approach with the aim of designing and developing new materials with excellent properties tailored to the demands of the special problems to be solved. For such materials design there are two basic needs: First, a profound knowledge of the relationship between composition, structure, and properties of a crystal, and secondly, a chemical playground where the probability of realizing theoretically designed structures is rather high. Concerning the first topic, a suitable and mostly successful model has been proposed by Chen et al.,[3134] called the theory of anionic groups. It is model for inorganic (borate) materials that is analogous to the principles used for organic NLO materials to calculate
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bulk NLO coefficients from molecular nonlinearities,[35] and is based on the relationship between the microstructure and bulk properties of a crystal. In inorganic compounds such as borates, the anionic groups are considered to be the most basic structural units responsible for optical nonlinearity, and their contributions can be summated to produce the bulk NLO properties. Therefore it should be possible to select structural units of existing inorganic compounds that possess favorable properties for the design of new compounds that also have excellent properties. Recently, even a computer-assisted NLO materials design system based on a combination of the principles of the theory of anionic groups with charge density distribution analysis and energy band calculations was proposed by Chen et al.[36] for the development of new materials with predictable coefficients dijk, Dn, and cutoff wavelength. For the second topic the large family of borate compounds is a suitable chemical playground now adopted by many materials scientists, because the extremely wide variability of borate crystal chemistry[37] allows the creation of very different structure types. Furthermore, among all the borate structures reported until now 36 % (!) are noncentrosymmetric while among the reported inorganic crystal structures there are in total only 15 % of noncentrosymmetric structure. Therefore, the probability that a new borate structure lacks a center of symmetry is more than twice as high than for non-borate structures. The first NLO borate described was KB5O84H2O[38] in 1975, but intense research on NLO borate materials began with the advent of low-temperature (b-)BaB2O4 (BBO)[3,4] and LiB3O5 (LBO),[15] which are up to now still by far the most frequently used NLO borate materials. A subsequent search for new borate compounds led to the continued discovery of new borate compounds with improved NLO properties (or in some cases NLO properties that are presumed to be good). Borates that are not only useful for frequency conversion but also as self-frequency-doubling active laser sources have been developed mainly based on the structure type of the mineral huntite CaMg3(CO3)4. Ordinarily, in these borates, carbon is substituted by boron, calcium by a rare earth element or yttrium, and magnesium by scandium, gallium, or aluminum. A commercialized self-frequencydoubling laser source of the huntite family is Nd:YAl3(BO3)4 (NYAB), but the problem that hinders its further mass application is mainly the unsatisfying homogeneity of the crystal owing to difficulties in crystal growth from the flux melt. To overcome this problem research is being carried out within and outside the field of the huntite-type borates in order to discover self-frequency-doubling laser crystals with better growth properties. Thus new borate laser materials with self-frequency-doubling potential have also been reported recently, namely, Nd:GdCa 4 (BO3)3O[39,40] and Yb:BaCaBO3F.[41] These materials do not adopt the huntite structure type and can be grown from the stoichiometric melt by the Czochralski method and
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from the stoichiometric melt with a slight excess of B2O3, respectively. Table 3 lists the most important NLO borate materials recently described in the literature.
Table 3. Borate materials used or suggested for nonlinear optical applications.

highly viscous melts have been studied in detail by Liebertz,[42] who presents, through examples, a rather simple but successful strategy. Crystals that do not melt congruently or that suffer a phase transition below the melting point can often be grown by the TSSG (top seeding solution growth) technique using a melt as the solvent. Fluxes can also be used to lower the viscosity of the melt. But, besides the problem of finding a suitable solvent, every deviation from stoichiometry of the melt reduces the utilizable amount of material to be crystallized, delays the growth period, and therefore becomes a question of growth economy. Furthermore, flux-grown crystals often tend to incorporate microinclusions of solvent, which drastically reduce the damage threshold.[43] Therefore great effort has been expended to improve the crystal growth process of borate NLO materials especially in the case of b-BaB2O4 and LiB3O5. A summary is given below. 3.1.1. b-BaB2O4

[a] Self-frequency-doubling laser. [b] Self-frequency doubling assumed. [c] Frequency doubling, laser activity assumed. [d] Laser and SHG properties assumed.

To summarize, three fundamental features of NLO borate materials have to be considered: 1) a crystal structure with an advantageous arrangement of highly NLO-active structural units, 2) suitable linear optical properties, and 3) the availability of crystals of sufficient optical quality and size through crystal growth processes. These features will be the subject of the following sections.

3.1. Crystal Growth The example of Nd:YAl3(BO3)4 in the previous section points out that one of the main limiting factors for application of NLO borate materials is the process of crystal growth. In most cases NLO borate materials are grown from melts, with the exception of KB5O84H2O, which is grown from aqueous solution. Crystal growth from melts is a very efficient and suitable method to obtain large single crystals of materials with congruent melting point. It becomes difficult, however, if the melts are of high viscosity, as is mostly the case for borate melts, as they tend toward glass formation at moderate or even low cooling rates. Since viscosity and diffusivity are reciprocally correlated, the mobility of the particles in the melt is strongly reduced. This results in problems of initial crystallization, which is needed to prepare a suitable seed crystal, and in extended growth periods. Therefore, application of the commonly used Czochralski technique needs special equipment to obtain very slow pulling rates of about 0.15 mm/day. The principles of crystal growth from 982
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Polymorphic b-BaB2O4 occurs in two forms: the high temperature (a-)phase, which is centrosymmetric (R3c),[44] and the non-centrosymmetric (R3c)[45] low-temperature (b-)phase, with a reversible but kinetically hindered phase transition near 925 C. In order to avoid the formation of the a-phase, in most cases b-BaB2O4 crystals are grown by the TSSG method to depress the melting point below 925 C. Early on large bulk single crystals of b-BaB2O4 were grown using Na2B2O4 as flux.[4547] A detailed analysis of the solvent systems for b-BaB2O4, including B2O3, BaCl2, BaF2, Li2O, Na2B4O7, and Na2O, has been carried out[48] as well as for NaCl, Na2SO4, and CaF2 fluxes.[49] Nowadays the best established fluxes are Na2O, NaF, and mixtures of both. Crystals grown from these melts obtain sizes of 4570 mm in diameter and 1020 mm in length.[5053] Other fluxes containing BaONa2O or NaCl led to similar crystal dimensions with very few inclusions only being reported.[54,55] To avoid flux inclusions completely, Czochralski growth from stoichiometric melts has also been attempted. Here a high temperature gradient near the melt surface has to be used in order to adjust a sufficient supercooling of the melt below the phase transition temperature to obtain b-BaB2O4 directly. Crystals grown by this technique are of up to 18 mm in diameter and 70 mm in length[56,57] but may be internally stressed due to the high temperature gradient applied. b-BaB2O4 for efficient waveguide-based frequency converters, modulators, and switches used as components for advanced integrated optic systems is also grown in thin films of about 3.55 mm. Several techniques are applied here, including the sol-gel method using metal alkoxides,[58] pulsed laser deposition,[59] and chemical vapor deposition (CVD),[60] with best results of high effective SHG coefficients of about 2.2 pm/V on sapphire (001) substrates,[59] comparable to that of bulk b-BaB2O4.
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3.1.2. LiB3O5 LiB3O5, initially reported in 1926,[61] crystallizes according to the phase diagram of the Li2OB2O5 system[62] by a peritectic reaction at 834 C to orthorhombic (Pna21)[63] crystals. At 595 C it decomposes to Li2B4O7 and Li2B8O13, but this reaction is reported to take a long period of time, so crystals of LiB3O5 cooled at moderate rates (3040 C/h) remain stable. The first successful growth of small crystals was achieved by the solid-state reaction of B2O3 glass covered with LiF powder and reaction at 750 C for 10 h.[63] Due to its incongruent melting, large bulk single crystals of LiB3O5 have to be grown by flux methods. From early on, a self-fluxed melt with excess B2O3 has mainly been used and the TSSG technique successfully applied. The composition of the used fluxes varies between Li2O:B2O3 = 1:3.8 to 1:5.6, and slow cooling rates of about 0.3 C/day are applied to allow the excess B2O3 to move away from the growing interface.[15,6467] Since LiB3O5 is reported to suffer from humidity, forming Li3B7O12[68] at high temperatures, some crystals have been grown in N2 flow.[67] Crystal sizes of 20 20 15 mm3 to 6070 mm diameter and 1015 mm length are obtained by these methods, but the crystals have not been characterized except to report that they are free of inclusions. In some cases in which the crystals were further analyzed, microinclusions consisting of B2O3, Li2B4O7, and Li2B8O13 are described. They are thought to be products of crystal decomposition during the cooling process.[69] A great problem with the growth of LiB3O5 from B2O3 fluxes is the rather high viscosity and the resulting low diffusivity of the melt. To reduce melt viscosity, fluxes such as LiF and MoO3 have also been applied, but offered no significant improvement in crystal quality.[70,71] Similar to growth experiments with B2O3 flux they show that special care is needed during cooling of the crystals, because LiB3O5 is very sensitive to thermal inhomogeneity and cracks very easily due to internal stress. 3.1.3. Congruently Melting NLO Borates One of the main disadvantages of BBO and LBO is their need to be grown from flux melts. Flux techniques in general assume longer growth periods, yield a smaller amount of crystallized material per unit volume of the crucible compared to Czochralski growth from the stoichiometric melt, and bear the risk of solvent inclusions. Therefore soon after the introduction of BBO and LBO as NLO materials, an intensive search for borate compounds with similarly good NLO properties but a congruent melting point began and led to numerous new NLO borate compounds. Usually they are grown by the Czochralski technique from the stoichiometric melt, which in most cases is prepared from prereacted, sintered powder mixtures with an appropriate composition of the starting materials.
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Among all the new NLO borate compounds, tetragonal (I42d)[72] CsLiB6O10, which is a structural derivative of LiB3O5, has been grown into the largest crystals. Grown by top seeding without crystal pulling but with an ACRT (accelerated crucible rotation technique) rotation of 15 rpm and only slightly supercooled beneath the melting point at 848 C, uncracked clear single crystals of dimensions 29 20 22 mm3 have been reported.[73] Using a melt with a deficiency of B2O3 (molar ratio Cs2O:Li2O:B2O3 = 1:1:5.5) at the saturation temperature 845 C, very large single bulk crystals of 140 110 110 mm3 with good optical quality could be grown by applying the same growth parameters.[74] Another derivative of LBO is orthorhombic (P212121)[75] CsB3O5, which was first described in 1958 as being a new compound in the system Cs2OB2O3[76,77] with a congruent melting point at 842 C. Large single crystals were grown along [010] by top seeding without crystal pulling at a slight initial supercooling of 0.3 C and a cooling rate of 0.2 0.5 C/day to a size of 20 12 12 mm3.[78] To further enlarge the resulting crystals, a slight excess of Cs2CO3 was successfully introduced to compensate for evaporation during the growth period and ACRT rotation was applied. Crystals were grown in a furnace with a low temperature gradient at the melt surface of about 1 C/cm at a cooling rate of 0.10.2 C/day. They obtain dimensions of 40 25 25 mm3 but no characterization of crystal quality is given. The same is true of crystals grown by the crystal pulling technique with a pulling rate of 8 mm/day, which reached a size of 20 mm in diameter and 30 mm in length.[79] Li2B4O7 crystallizes in I41cd[80] and occurs as a congruent melting phase in the system Li2OB2O3 with a melting point at 917 C. It was prepared as single crystals by fusing stoichiometric amounts to a glass and subjecting the glass to further heat treatment between 800 C and 900 C.[80] Large single crystals were grown for application as a surface acoustic wave (SAW) substrate after the report by Whatmore et al.[81] Later, the NLO properties of Li2B4O7 were also reported.[82] It can be grown by the Czochralski technique with a crystal rotation of 410 rpm while a linear growth rate of about 0.6 mm/h can be achieved. Single crystals of up to 15 mm in diameter and 50 mm in length,[42,82,83] and 35 mm in diameter and 40 mm in length[84] were successfully pulled. Crystals with a small number of dislocations (100/cm2, analyzed by X-ray topography) and a homogeneity of refractive index of better than 106/mm (interferometric study) were grown with a diameter of 5060 mm by using a seed crystal orientated parallel to [110].[19] The isostructural borates SrB4O7 and PbB4O7, both of which have the orthorhombic space group symmetry P21nm,[85] were produced as small needle-shaped single crystals by fusing stoichiometric powder mixtures.[85,86] Large single crystals of PbB4O7 were grown by the Czochralski technique from a melt with a slight excess of PbO to lower the viscosity of the melt (3435 mol.-%
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instead of 33.3 mol.-%) at 774 C. A seed orientation of [100] or [001] is advantageous, as [010] was found to be the direction of smallest growth velocity. Growth runs, with a cooling rate of 0.7 C/day and a pulling rate of 04 mm/day without rotation, produced single crystals of up to 20 28 55 mm3. In the outer regions, the crystals were disturbed by gas inclusions, but the larger part of the crystals was of optical quality.[42] In the same manner, large single crystals of SrB4O7 were grown from prereacted stoichiometric melt at 994 C. With seed crystals orientated parallel to [001], clear crystals 25 mm in diameter and 20 mm in length were grown using pulling rates of 2 mm/day0.2 mm/h and a crystal rotation of 20 rpm.[87,88] A rather new family of NLO borates is monoclinic (Cm)[40] MCa4(BO3)3O with M = Y, Gd. The family of RECa4(BO3)3O, where RE = La, Nd, Sm, Gd, Er, Y, was first synthesized as small crystals by Norrestam et al.[89] and the compounds with Y and Gd were subject to crystal growth experiments. GdCa4(BO3)3O melts at 1480 C and can be grown by the Czochralski technique from prereacted (at 1350 C) melt with a growth rate of about 1 mm/ h and a 3040 rpm crystal rotation. Crystal sizes of up to 2030 mm in diameter and 70 mm in length can be obtained.[39,40,90] Crystals of GdCa4(BO3)3O are reported to be perfectly transparent but to sometimes have (201) or (010) cleavage plates[39] and to contain inclusions of bubbles.[90] Growth of YCa4(BO3)3O with a melting point at 1510 C by a similar technique resulted in clear crystals without cracks, with dimensions up to 25 mm in diameter and ~25 mm in length. Like GdCa4(BO3)3O these crystals also show inclusions of bubbles.[90,91] A very new borate compound for potential NLO applications, BaCaBO3F, has been reported recently by Keszler et al.[92] Doping of the Ca sites with Yb leads to IR laser emission and the material is suggested to be a selffrequency-doubling laser. Large single crystals of Yb:BaCaBO3F can be grown by the Czochralski technique from a melt prepared in two steps to avoid the formation of Ba and/or Ca peroxides. First BaCa2(BO3)2 is synthesized by sintering of a stoichiometric powder mixture, then BaF2 and YbF3 are added to form a stoichiometric melt. Crystals grown with a pulling rate of 2.5 mm/day and 470 rpm rotation reached dimensions of 25 mm in diameter and 30 mm in length but were fractured. All of the crystals grown so far show inclusions and growth striations.[41] Some further borate compounds, introduced as potential NLO materials, were grown only in small crystals of some tenths of a millimeter in size. Crystals of BaZn2(BO3)2 and Ba2Zn(BO3)2 are grown from their stoichiometric melts simply by slow cooling to solidification. The former melts at 980 C and is obtained by cooling at a rate of 1.5 C/h to 860 C;[93] the latter melts at 1050 C and forms by cooling at a rate of 6 C/h to ~600 C.[94] The specimens CaBa2(BO3)2 and Ca5Ba2B10O22, occurring in the CaOBaOB2O3 system, are grown by solid-state reaction of stoichiometric mixtures of B2O3, BaCO3, and CaCO3 at 7801040 C.[95] 984
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3.1.4. Incongruently Melting NLO Borates The aim of creating new borate compounds with high SHG coefficients by the application of the theory of anionic groups led to compounds with (nearly) planar [BO3]3 groups as basic structural units, either as isolated triangular [BO3]3 or coupled to pairs of [B2O5]4 groups. The family MBe2BO3F2, with M = Na, K, is an example of a structure type with isolated [BO3] triangles, crystallizing in the non-centrosymmetric space group R32.[96] The potassium compound KBe2BO3F2 was first synthesized by scientists in the Soviet Union in 1968[97] and large single crystals were grown from flux melts with KBF4 and BeO. No details of the growth procedure and the melt composition are reported, but the resulting plate-like crystals reach dimensions of up to 10 10 0.3 mm3.[96,98,99] NaBe2BO3F2 was grown from a flux melt, which is not further specified other than as containing NaBF4 and BeO, by cooling the melt at a rate of 10 C/day. The crystals obtained are small (about 0.1 0.4 0.6 mm3).[100] Improvement of the NLO properties by enhancing the number of NLO-active [BO3] groups per unit volume of the crystal structure was attempted by creating Sr2Be2B2O7. The hexagonal (P6c2)[101] crystals were grown by the high-temperature TSSG technique, but no information is reported about the growth parameters and the exact composition of the melt apart from the use of SrB2O4 as flux. Crystals grown within 1050 C1100 C by slow cooling (12 C/day) obtained dimensions of 7 7 3 mm3 and were reported to be of good optical quality.[101,102] The potential NLO borate Ca5(BO3)3F with isolated [BO3] triangles as NLO-active groups and monoclinic space group symmetry Cm[103] is only grown as small crystals by the flux method from a melt containing CaCO3, H3BO3, and CaF2, but no further details are reported.[103] The family of the pyroborates ANbOB2O5, with A = K, Rb, Cs, crystallizing in Pna21 (for A = K)[104,105] and Pnm21 (for A = Rb,[106] Cs[107]), possesses [B2O5] groups as basic structural unit besides chains of [NbO6] octahedra. The compounds melt incongruently, and melts with K2B4O7, Rb3B3O6, and Cs3B3O6 as fluxes exhibit high evaporation rates of the added solvent, causing severe problems with crystal growth. Crystals of KNbOB2O5 and RbNbOB2O5 were grown by the TSSG technique with initial melt compositions A2CO3:Nb2O5:B2O3 = 1:2.8:6.2 (A = K, Rb) and cooling rates from 0.1 C/day[104] to 8 C/day,[105] resulting in crystal sizes up to 8 10 3 mm3 for RbNbOB2O5 and 2 2 5 mm3 for KNbOB2O5.[104] The crystals grown usually show (100) cleaved plates, which limits the obtainable size of the crystals. 3.1.5. Borates of the Huntite Type As early as 1962 numerous borates with a structure similar to the structure of the mineral huntite were synthesized, the families of RAl3(BO3)4, with R = Y, Nd,
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Sm, Eu, Tb, Dy, Ho, Yb, and Er, and RX3(BO3)4, with R = Gd, Sm, X = Cr, Al, and their bright, sharp-lined fluorescence were noticed.[108] All these huntite borates melt incongruently and have to be grown from flux melts. Successfully used melts were K2SO4 + 3 MoO3 or PbF2 + 3 B2O3.[108] All the crystals are trigonal with space group R32.[108] Most of the above compounds have also been synthesized from a series of flux melts, including BaO B2O3, BaOB2O3BaF2, PbOB2O3, Li2B4O7B2O3, and K2SO4MoO3.[109111] Nowadays, the best established flux is K2Mo3O10 because this solvent dissolves the huntite-type borates at moderate temperatures and the resulting melts are of low viscosity. The most commonly used huntite-type borate is Nd:YAl3(BO3)4 (NYAB), first discovered in 1981,[112] which can be used as a self-frequency-doubling laser crystal to generate green laser output. It can be grown from molybdate flux by the TSSG technique with slow cooling at a rate of 2 C/day and ACRT rotation, using a [001] seed, to dimensions up to 20 20 35 mm3.[113,114] Unfortunately, the crystals of NYAB grown generally show defects such as growth striations, growth section boundaries, dislocations, and inclusions. Furthermore they occasionally form Brazil twins.[114] In the search for new selffrequency-doubling laser crystals that are more easy to grow, the GdAl3(BO3)4, SmAl3(BO3)4, and HoAl3(BO3)4 components were synthesized, but to date only small crystals have been grown.[114] Yb:YAl3(BO3)4 was grown, similar to NYAB, as large single crystals from molybdate flux, with improved crystal quality compared to NYAB, but unfortunately no details of the growth process and the obtained crystal size are reported. Dislocations were detected by etching of the crystal faces.[114] Nd:GdAl3(BO3)4, also capable of use as a self-frequency-doubling laser crystal, was grown from molybdate flux with 80 % solvent by the TSSG method into crystals with parts of good optical homogeneity 3 7 7 mm3 in size.[115] A further expansion of the huntite family led to M(Al,Ga)3(BO3)4, with M = Yb, Er, Ho, Bi, grown from Bi2O3B2O3 flux into small crystals of about 0.1 mm in size.[116] Single crystals of YAl3(BO3)4 and GdAl3(BO3)4 of larger size (8 5 10 mm3) could be grown from molybdate flux by using low frequency vibration of the crystal instead of rotation to stir the melt during crystal growth, which improved the crystal quality significantly.[117] NdAl3(BO3)4, Nd(Ga,Cr)3(BO3)4, and Nd:LaSc3(BO3)4 are huntite-type borate laser materials not only used as bulk crystals but also as thin-film materials for construction of microchip lasers.[118121] Thin-film borates with thicknesses between 50 and 220 mm are prepared by liquid-phase epitaxy (LPE) from molybdate flux on laserinactive substrates, e.g., Gd0.59La0.41Ga3(BO3)4.[120,121]

specific frequency converting materials continues. In terms of materials that are reasonably well developed today, the materials for NLO application in the IR (~220 mm) are chalcopyrites (e.g., AgGaSe2, ZnGeP2), for the visible and near UV materials such as KNbO3 and KTiOPO4 are used, and for VUV (vacuum ultraviolet) and visible mainly borates such as BBO and LBO are suitable. Considering the commercial success of BBO and LBO, many efforts toward the development of new NLO borates are concentrated on materials having complementary properties to those of LBO and BBO or improved properties, for example, better crystal growth behavior. Some of the main aims of the development of new borates have been the production of materials with relatively large SHG coefficients dijk, moderate birefringence, short UV cutoff, and congruent melting. These features have more or less been realized in some of the materials listed in Tables 47. The rather well-analyzed properties of BBO and LBO as well as those of KB5O84H2O are given in detail in the Handbook of Nonlinear Optical Crystals,[122] where readers interested in further data (about non-borate NLO materials as well) are referred to. All the values in Tables 47 are given for 1064 nm wavelength unless otherwise indicated.

3.3. Structural Considerations Over the last ten years, many efforts have been made to understand the relationship between the composition, structure, and NLO properties of materials, which plays the key role in the search and design of new NLO materials. One of the most suitable models was developed by Chen et al.,[31 34] the theory of anionic groups, which is based on two fundamental assumptions: 1) The anionic groups in the crystal structures are mainly responsible for the NLO properties and the observed bulk NLO susceptibility tensor of a crystal is the geometrical superposition of the microscopic NLO susceptibilities of the anionic groups. Contributions from highly coordinated, rather spherical cations are regarded as being negligible. 2) The microscopic secondorder susceptibilities of the anionic groups can be calculated from the localized molecular orbitals of the group by approximation methods used in quantum chemistry. The reliability of this approach has been proved by the continuous discovery of new NLO borates, for example, KBe2BO3F2 and Sr2Be2B2O7. However, it should be noted that borate anionic groups, especially [BO3]3, generally do not show the idealized high symmetry assumed in theoretical approaches. As a result of the analysis of 75 borate structures, Zobetz[139] pointed out that no borate crystal structure could be found with [BO3] groups of symmetry 6m2 (D3h) or even mm2 (C2v). The most frequent symmetry (found for 76 % of all structures analyzed) of [BO3] units is in fact 1 (C1). Therefore, SHG coefficient calculation could possibly be improved by using the real symmetry of anionic groups.
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3.2. Nonlinear Optical Properties Because of the continuing demand for new laser systems with unique wavelength and high power, the quest for new
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Table 4. Selected properties of several nonlinear optical borate materials.

Table 5. Selected properties of several nonlinear optical borate materials (continued from Table 4).

Favorable structural units with large nonlinear susceptibilities are, for example, [BO3]3, which forms delocalized p-type bonds perpendicular to the [BO3] plane, and strong covalently bonded systems with large bond polarizability such as [TiO6]8 or [NbO6]7. 986
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Besides the microscopic nonlinear susceptibilities of the NLO-active structural units, the orientation of these structural units within the unit cell and their number per volume of the unit cell influence the bulk NLO properties as well. For example, a large number per unit volume of
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Table 6. Selected properties of several nonlinear optical borate materials (continued from Tables 4 and 5).

Table 7. Selected properties of several borate materials suggested for nonlinear optical application.

these chromophores together with their coparallel alignment and a favorable orientation of the groups within the crystal structure are thought to produce high nonlinear bulk susceptibilities. Therefore, the relationship between the macroscopic SHG coefficients dijk and microscopic
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nonlinear susceptibilities blmn can be expressed according to Equation 3, where fi = (n2 + 2)/3 and the R values are i the direction cosines. These structural requirements are also correlated with the optical birefringence of the crystal, which determines the second essential optical
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property for effective NLO materials, the phase-matching behavior. fi fj fk V

lmn

dijk

blmn Ril Rjm Rkn

(3)

Since borate compounds containing only [BO3] groups can achieve UV transparency down to ~160 nm, many orthoborates and related compound have been synthesized. In b-BaB2O4, [BO3] groups are condensed to [B3O6] ring groups and have their plane orientated perfectly perpendicular to the polar three-fold axis. The ring groups are slightly rotated around the three-fold axis by angles of either ~9 or ~20 to the glide plane (Fig. 2), thus reducing their alignment and, to some degree, the nonlinear coefficient d22 value theoretically possible with perfect alignment.[92]

Fig. 3. Details of the arrangement of [BO3] and [BeO4] groups in the crystal structure of Sr2Be2B2O7, viewed along the c-axis. Large light gray spheres represent O atoms, smaller dark gray spheres B atoms and small black spheres Be atoms. Sr atoms are left out (data from [101]).

Fig. 2. Details of the borate groups arrangement in the crystal structure of bBaB2O4, viewed along the c-axis. Dark gray spheres represent B atoms, light gray spheres O atoms. Ba atoms are left out (data from [140]).

A similar misalignment is observed in Sr2Be2B2O7, where [BO3] groups are linked, through [BeO4] tetrahedra by sharing corners, to sheets, which are stacked with coplanar orientation along [001]. With respect to the polar diad axis of the structure they are rotated by an angle of ~24 (Fig. 3), while in KBe2BO3F2, where [BO3][BeO3F] sheets are very similarly stacked along [001], the [BO3] groups are perfectly aligned along the polar axes a1 and a2 (Fig. 4). A structural comparison of these compounds to explain the magnitude of their SHG coefficients is shown in Table 8 by taking the chromophore density (i.e., [BO3] per unit volume, e.g., 1000 3) of identical chromophores with similar coplanar orientation and the refractive factor 988
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Fig. 4. Details of the arrangement of [BO3] and [BeO3F] groups in the crystal structure of KBe2BO3F2. Large light gray spheres represent O atoms, large dark gray spheres F atoms, smaller dark gray spheres represent B atoms, and small black spheres Be atoms. K atoms are left out (data from [96]).

(n2 + 2)2(n2 + 2) into account (as proposed by Mei and o e Ishizawa[141]). For Sr2Be2B2O7 the measured nonlinearity is reduced by 20 % compared to the calculated value. Considering the structural differences between KBe2BO3F2 and Sr2Be2B2O7 this effect may be assigned to the misalignment of the
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Table 8. Comparison of BBO, SBBO, and KBBF with respect to the ratios of their SHG coefficient, chromophore density, and refractive factor. [B3O6] rings are thought to equal 3 [BO3], therefore d22 of BBO is enhanced by a factor of 1.2, values of KBe2BO3F2 are set to unity.

[BO3] groups in Sr2Be2B2O7, but for b-BaB2O4 this simple model does not hold. The discrepancy between the expected value, which should have a comparable deviation from the measured value as for Sr2Be2B2O7 (since the misalignment is comparable), and the calculated value can possibly be explained by a non-negligible contribution from the [BeO3F] tetrahedrawhich link the [BO3] groups of KBe2BO3F2 and Sr2Be2B2O7 to sheets and which are also similarly aligned to the macroscopic nonlinearity of the crystal. In Ba2Zn(BO3)2 a very similar feature can be observed, here planar [BO3] groups are linked in a similar manner as in KBe2BO3F2 by [ZnO4] tetrahedra to sheets parallel to (001) (Fig. 5a). Within these sheets, the [BO3] groups are almost perfectly aligned along the polar c-axis, deviating only by ~4 from the [001] direction (Fig. 5b). Between these zinc borate sheets are layers of [BO3] groups with their triangular planes only very roughly oriented perpendicular to [001]. The calculated maximum SHG coefficient d24 of Ba2Zn(BO3)2 equals 0.61;[94] comparing this value to d11(KBBF) = 1.3 d24(Ba2Zn(BO3)2) (where KBBF is KBe2BO3F2) and regarding the chromophore density of KBBF as being 1.56 times that of Ba2Zn(BO2)2, this value seems to be quite reasonable, as pointed out by Smith and Koliha.[94] Considering the layers of poorly oriented [BO3] between the zinc borate sheets to be responsible for the NLO properties[141] seems likely to be wrong. Surveying the known crystal structures of NLO borates, the favorable orientation of conjugated groups such as [BO3] seems to be parallel and not perpendicular to the polar axis of the structure. b-BaB2O4 is the only reported case where the [BO3] planes lie normal to the polar three-fold axis, while, for example, for SBBO (Sr2Be2B2O7), KBBF, and YAB,[143] the polar axes are parallel to the planes of the [BO3] groups. Crystal structures with all the [BO3] groups orientated in a coplanar manner normally produce large birefringence (which causes high angular sensitivity of phase matching), show good to excellent cleavage parallel the planes of [BO3], and cause difficulties in crystal growth due to their more or less pronounced sheet habit. In order to reduce these effects derivatives of SBBO were synthesized, for example, BaAl2B2O7, where the layers of [BO3] groups are linked through bridging oxygen atoms bonded to aluminum atoms of adjacent layers.[36] Other possibilities are the introduction of more roughly orientated [BO3] groups into the crystal structure as done for Ba2Zn(BO3)2 or a combination of [BO3] and [BO4] structural units.
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Fig. 5. a) Arrangement of [BO3] and [ZnO4] groups within the unit cell of Ba2Zn(BO3)2, viewed along [010]. b) One sheet of linked [BO3] and [ZnO4] groups, viewed along [100]. Large light gray spheres represent O atoms, smaller dark gray spheres B atoms, and small black spheres Zn atoms. Ba atoms are left out (data from [94]).

A promising crystal family (because crystals of good quality can easily be grown) with a less coplanar stacking of some of the [BO3] groups is the recently reported MCa4(BO3)3O (M = Y,Gd). These compounds are derivatives of the previously described Ca5(BO3)3F. The Y and Gd compounds are isostructural[90] and contain two types of [BO3] groups. One third of the [BO3] groups per unit cell
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are stacked in a coplanar manner along the c-axis and perfectly aligned parallel to the a-axis, while for two thirds of the [BO3] the normal to the [BO3] plane is skewed toward the c-axis by ~30 and they are rotated by ~13 off the a-axis (Fig. 6a,b). With this arrangement (which can similarly be found in Ca5(BO3)3F[103]) the birefringence is reduced to a moderate value of 0.04 and the mechanical stability of the crystals is enhanced compared to sheet structure types. An effective nonlinearity, deff, (1064 nm, type I phase matching) of 1.11.3 pm/V can be achieved, which is about one half of that of BBO.

Fig. 7. Details of the arrangement of [BO3] and [BO4] groups, condensed to [B4O9] rings, in the crystal structure of Li2B4O7. Large light gray spheres represent O atoms, smaller dark gray spheres B atoms. Li atoms are left out (data from [80]).

b)

melting compounds CsB3O5, CsLiB6O10, and Li2B4O7 can easily be grown to large single crystals of good quality. On the other hand, due to their birefringence of 0.030.05, deep UV generation can not be obtained. Attempts were made to design a borate material with comparable nonlinearity to that of KTP (KTiOPO4) by combining planar [BO3] groups with highly polarizable [NbO6] octahedra. Pyroborates of the type ANbOB2O5, with A = K, Rb, Cs, were formed, where the cesium compound adopts the parent structure of the crystal family,[104] while the other members exhibit superstructures of this basic type. The structure contains [B2O5] groups in a coplanar stacking parallel to (100), which link chains of [NbO6] octahedra running along [100] (Fig. 8). In CsNbOB2O5 the [B2O5] are fairly well aligned along the c-axis, while for the other compounds they are tilted according to a zigzag tilting of the

Fig. 6. a) Arrangement of [BO3] groups within the unit cell of GdCa4(BO3)3O, viewed along the c-axis. b) View perpendicular to that in (a), along the a-axis. Large light gray spheres represent O atoms and smaller dark gray spheres B atoms. Gd atoms and Ca atoms are left out (data from [142]).

The introduction of [BO4] tetrahedra into a borate structure is realized in NLO borates by formation either of [B3O7] or [B4O10] rings and leads to crystals such as LiB3O5, CsB3O5, CsLiB6O10, or Li2B4O7. In their structures, the borate rings are arranged around the c-axis and tilted by an angle of about 45 (Fig. 7). As pointed out by Chen et al.[15] and Uda et al.,[19] and can be seen from Tables 3 and 4, these groups are ideal basic structural units from the point of view of absorption edge, SHG coefficient, as well as damage threshold. Furthermore the congruent 990
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Fig. 8. Arrangement of [B2O5] and [NbO6] groups within the unit cell of CsNbOB2O5. Large light gray spheres represent O atoms, smaller dark gray spheres B atoms, and small black spheres Nb atoms. Cs atoms are left out (data from [107]). 0935-9648/98/1309-0990 $ 17.50+.50/0 Adv. Mater. 1998, 10, No. 13

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[NbO6] octahedra owing to the formation of superstructures. Unfortunately, the chains of [NbO6] octahedra are orientated perpendicular to the polar c-axis and do not contribute to the nonlinearity of the material and therefore a rather low nonlinear optical effect of about five times that of KDP is observed by powder SHG measurements.[105] Due to the most perfect alignment of the [B2O5] groups in CsNbOB2O5 the largest nonlinearity is to be expected here; however, powder SHG measurements carried out in our laboratory on this crystal family resulted in almost identical nonlinearity for all three compounds.[144]

4. Conclusions
The design of borate materials by careful choice of favorable anionic groups that are able to produce high nonlinearities and a suitable birefringence is a mostly successful method for obtaining new excellent NLO materials. However, no model is available to estimate whether the first basic requirement for NLO materials, i.e., non-centrosymmetry, will be fulfilled by a new material before it is grown. Therefore, we have to consider all of the known borate structures. An analysis shows that there are several types of compounds in which the sharing of noncentrosymmetric structures is significantly above average. The most pronounced tendency to form non-centrosymmetric structures is shown by compounds of the type AM3(BO3)4, which are mostly derivatives of the huntite structure type, with 70 % having non-centrosymmetric structures. 58 % of the compounds of the type A3M2(BO3)2 are non-centrosymmetric; they are mostly derivatives of the shortite structure type. As pointed out by Xia,[145] compounds of the type MmA2(BO3)Xn, where M is a cation with coordination number (CN) greater than four, A is a cation with CN = 4, and X = O, OH, F, etc., are also favored to obtain non-centrosymmetric structures. Keszler et al.[92] remarked on borates containing [B3O7] groups that they prefer non-centrosymmetric structures because the [B3O7] group in borate structures in most cases becomes slightly distorted and stacks helically. These aspects should be kept in mind when designing new NLO borate materials. Secondly, NLO borate materials all belong to the conjugated group type except for SrB4O7 and PbB4O7, while other NLO materials such as KTP and LiNbO3 are of the deformation type, with alternating longshort MO bonds. So the idea arises to design either borate compounds that contain strongly distorted [BO4] tetrahedra such as SrB4O7 but to arrange them in chains to produce (positive) birefringence, or compounds with distorted [BO3] groups with one elongated BO bond and to align them parallel to one crystallographic direction. Although there are some practical difficulties, according to these ideas a way to design a new type of NLO borates might possibly be opened.
Received: March 4, 1998 Final version: April 28, 1998

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