Characterization of KDP crystal grown from solution with low pH value

Solubility curves of KDP (KH₂PO₄) in solutions with different pH values were measured. It was found that the solubility of KDP crystal increased with the reduction pH value of solution. Transparent KDP crystal was grown from solution with 1.5 pH by point seed. Chemical etching experiments revealed that pyramid sector of the crystal displayed more growth defects. Growth defects, such as growth striation and inclusion, were analyzed by white‐beam synchrotron radiation X‐ray topography. The reasons for the formation of these growth defects were discussed. Transmittance spectra test of both prismatic sector and pyramidal sector was performed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and mechanical properties of KН2PО4 single crystals with embedded nanoparticles and organic molecules

Single crystals of KDP crystals with embedded Urea molecules and TiO₂ nanoparticles have been grown from aqueous solution by the temperature lowering method. The effect of the organic molecules and nanoparticles on the structural and mechanical properties has been studied. It has been observed that addition of Urea molecules improves laser induced damage threshold and mechanical strength of the crystal, while TiO₂ nanoparticles have the opposite effect. The structure and composition of KDP:Urea crystal are studied by three‐crystal X‐ray diffraction analysis, which reveals the existence of a correlation between the increase of the microhardness value and the change of the crystal lattice parameter. The surface features of KDP:TiO₂ crystals are analyzed by scanning electron microscopy that reveals the presence of quasi‐equidistant growth bands caused by capture of the nanoparticles. It is shown that the rise of TiO₂ nanoparticles concentration up to 10⁻⁴ wt.% and higher resulted in 3‐fold reduction of the laser damage threshold of KDP:TiO₂ relative to pure KDP in [001] and [100] crystallographic directions. It is found that microhardness and fracture toughness decrease at the nanoparticles concentration of 10⁻³ wt.% due to crack formation at crystal lattice discontinuities. The grown crystals also have been subjected to dielectric studies.     

Structural features of the KH<Subscript>2</Subscript>PO<Subscript>4</Subscript>: Cr single crystal

The precision X-ray structural investigation of KH₂PO₄ (KDP) crystal samples from different growth sectors of a single crystal containing chromium impurities is performed. It is demonstrated that the structure of the sample from the prismatic growth sector is more perfect than the structure of the sample from the pyramidal growth sector. The impurity trapping can lead to the formation of at least four different types of structural defects on the face of the pyramid, whereas only two of them can be formed on the face of the prism. A comparison with the relevant data for the “pure” KDP crystal shows that the number of defects and their character are approximately identical for all samples. The analysis of the IR spectra indicates that nitrate ions are contained in the samples from both growth sectors. Moreover, structurally bound water molecules and OH groups are revealed in the sample from the prismatic sector.     

Enhancement of stability of growth,structural and NLO properties of KDP crystals due to additive along with seed rotation

Potassium Acetate (CH₃COOK) and Potassium Citrate (K₃C₆H₅O₇) as new additives were added into the potassium dihydrogen phosphate (KDP) solutions in different molar ratios. The metastable zone width and induction period with and without these additives were determined and compared. Dielectric measurements on pure and doped KDP crystals at various temperatures ranging from 313 to 423 K were carried out by the conventional parallel plate capacitor method which results low dielectric constant value dielectrics in doped crystals. The high resolution XRD studies show that CH₃COOK doped KDP crystal and K₃C₆H₅O₇ doped KDP crystal do not contain any internal structural grain boundaries and indicates that the crystalline perfection is very good. Moreover, the addition of these potassium additives improves the quality of the crystal and yields highly transparent crystals with well defined features. The effect of additives on the growth, nucleation kinetics, structural, NLO and optical properties has been investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth mechanism of crystals from aqueous solutions

Microscopic processes occurring on the surface of a growing crystal or a dissolving one were observed by microcinematography. The crystals under observation were grown either in a drop of solution by evaporation or in a constant-temperature microscope stage at a chosen supersaturation. Small (approx. 0.1 mm) and large (approx. 10 mm) crystals of NaCl, Pb(NO₃)₂, NaNO₃, CdI₂, KDP and ADP were studied. It is concluded qualitatively that the layers, in general polygonal, originating in one or several active centres, are formed on the crystal face, never at the corners or edges. – The average velocity of layer motion was studied quantitatively in dependence on their thickness and supersaturation. The layer motion at constant supersaturation considerably fluctuated. – Surface patterns created by moving layers agree in most cases with predictions of the dislocation theory. Two categories of steps were found on the surface: ”︁real”︁ macrosteps and shock waves. – The velocity of layer motion for most compounds lies within (1–10) · 10⁻⁴ cm · s⁻¹.     

Raman Study of Lattice Vibration Modes and Growth Mechanism of KDP Single Crystals

The space group theoretical analyses and assignment of the lattice modes of the KDP crystal have been made, and the Raman spectra of their growth solution have been observed in different growth regions. The attention is focused on the analysis of the 912 cm^‐1 band arising from the H₂PO₄^‐ anions in the interface between the KDP crystals and their growth solution. This has been assigned to the asymmetrical stretching mode of the deformation P(OH)₂ . From these results, the growth units of KDP crystal has been concluded to be the dimers of H₂PO₄^‐ anions. We consider that the result presented here is an important step towards the development of more complete crystal growth theories.     

Growth imperfections in oriented grown KDP crystals by X‐ray topographic analysis

Potassium dihydrogen phosphate (KDP) crystals were restrained to grow in two dimensions only, using a specially designed platform. This enables us to grow the blanks of frequency conversion elements that satisfy type‐II phase matching direction out of a type‐II phase‐matched seed crystal. Synchrotron radiation topography was used to study the growth mechanism of these profiling grown KDP crystals. It is found that both dislocation growth mechanism and layer growth mechanism were involved in the growing process. Inclusions, growth striations and dislocations were the main defects that influenced the crystalline quality of these crystals. High‐resolution X‐ray diffraction was employed to study the lattice integrality of the crystal.     

Study on rapid growth of KH2PO4 and its characterization

Large size crystals of KH₂PO₄ (KDP) were grown by adopting rapid growth technique from point seeds in a 1500‐liter crystallizer which is used to grow KDP crystals by conventional method. The grown KDP crystal size can reach to 310 × 310 × 320 mm³ and the average growth rate was 8mm/day. The optic properties of the rapidly grown KDP crystals were characterized comparing with the KDP crystals grown by the traditional temperature reduction method. We found it that the optical quality of the KDP crystals we grown rapidly are not significantly different from those of KDP crystals grown by traditional method. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

KDP(KD*P)晶体结构研究进展

本文回顾了70多年来人们对KDP(KD*P)晶体结构的研究成果,尤其对近年来在晶体表面界面结构、氢键结构等方面所取得的重大突破进行了综述,并力图强调晶体性能对结构的依赖关系.KDP晶体的表面及界面结构对于晶体的生长及缺陷的形成具有重要影响.表面X射线衍射研究结果表明:水溶液中的KDP晶体表面上有四层特殊结构的水分子层,前两层水分子象冰层一样牢固地结合在晶体表面上,后两层相对弥散.     

Influence of La3+ ions on growth and NLO properties of KDP single crystals

Single crystals of pure and Lanthanum added KDP crystals were grown from aqueous solution. The influence of La³⁺ ions in KDP crystals is studied. Isolated centers are formed by La³⁺ ions in KDP structure along (100) plane. La³⁺ ions incorporated into superficial crystal growth layer and slightly affect the growth process as they generate weak lattice stresses. The creation of these weak lattice stress is confirmed by Vickers's micro hardness test. The HRXRD analysis showed reduced structural defects in the La added KDP in the (100) plane than pure KDP. The incorporation of La in the crystal was confirmed by EDAX analysis. The Kurtz's powder SHG efficiency was found to be 1.5 times that of pure KDP. The UV‐Vis transmission spectra of La added KDP showed excellent transmittance from 1100 nm to 340 nm and did not show any change in lower cutoff wavelength with respect to pure KDP. Laser damage threshold value has been determined using Q‐switched Nd:YAG laser operating at 1064 nm and with 65 ns pulses in single shot mode. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microscopic studies on imperfections in selected YAB single crystals

The as‐grown surface and inner structures of undoped and Nd³⁺‐, Cr³⁺‐, V³⁺‐, Ce³⁺‐, Er³⁺ and Yb³⁺ – and (Er³⁺ + Yb³⁺) – doped yttrium aluminum borate (YAB) single crystals grown from (K₂Mo₃O₁₀ + B₂O₃) flux by spontaneous crystallization or top seeded solution growth (TSSG) technique, were investigated using optical and scanning electron microscopic and analytic chemical methods. Fine and rough growth hillocks of dislocational origin, growth layers, traces of inner planar defects and foreign phase crystalline debris were found and analyzed on the as‐grown faces of crystals. Irregular grains and regular block structures and foreign phase inclusions were observed and studied in the interior of the crystals. The chemical compositions measured by energy dispersive X‐ray spectrometry on perfect and imperfect micro regions are compared with those obtained by flame atomic absorption spectrometry on bulk crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization of benzimidazole by solution growth method and its characterization

The potential organic NLO crystal of benzimidazole (BMZ) has been successfully grown by slow evaporation solution growth technique at room temperature. The crystalline perfection has been verified by High resolution X‐ray diffraction (HRXRD) analysis. The very low angle boundary obtained for this solution‐grown specimen may be attributed to the segregation of solvent molecules (methanol), which were entrapped within the crystal during growth. The laser damage threshold has been measured by using high intensity Q‐switched Nd:YAG laser. The observed value is greater than that of KDP and lesser than that of melt grown benzimidazole. The NLO efficiency has been determined and it is compared with the KDP crystal. The thermal behaviour has been assessed by TG/DTA analysis. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The heteroepitaxial growth of KDP/ADP

Crystal growth rules of mixture crystals KADP (potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate (ADP)) have been analyzed based on the solubility product principle. The heteroepitaxial layers have been obtained by immersing KDP (ADP) substrate into the ADP (KDP) saturated solution at 313 K. The micromorphology indicates that small growing points on different planes show the self‐similar property compared to the bulk crystal's morphology. The process of epitaxial growth depends on not only form the lattice match but also form crystallizing kinetics which is the main influencing factor. Moreover, it can infer from the micromorphology on the surface of the mixed crystal that the dissolving of substrates will form mixed solution on epitaxial surface. What's more, corrosion phenomenon gets more and more evident with increasing times of epitaxial growth and it will be harder to form transparent epitaxial layers due to the increasing tension of epitaxial layers. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

快速生长KDP晶体表面的光学显微实时观察

设计了一套溶液降温法晶体生长显微实时观察装置,对快速生长KDP晶体{101}和{100}表面形貌的演化过程进行了实时观测分析.测量了晶体表面生长层切向生长速度随溶液过饱和度的变化曲线,并利用台阶生长动力学方程计算了相关动力学参数.进行了Fe3+掺杂实验,结果表明Fe3+的存在会影响到不同晶面上生长层的动力学系数,从而改变KDP晶体表面生长层的切向生长速度.     

Distribution of metallic ions in a single KDP crystal grown from aqueous solution

A single KDP (potassium dihydrogen phosphate) crystal was grown in a supersaturated solution containing a metallic ion (Al³⁺, Fe³⁺, or Cr³⁺). The growth rate, morphology, and distribution of the metallic ions into the KDP crystal were measured as the ionic concentration and supersaturation in the solution changed. It was found that in the KDP crystal, Al³⁺ and Fe³⁺ were greatly concentrated, but Cr³⁺ was diluted. Complete expressions for the effect of metallic ions on all aspects of the growth of KDP crystal were suggested. The growth rates of (100) and (101) faces were well correlated by the empirical equation and resulted in good estimation of morphology. The distribution of metallic ions into KDP crystal was also correlated by the distribution model. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of SiO32‐ impurity on growth habit of potassium dihydrogen phosphate crystal

By altering the concentration of silicate (SiO₃^2‐) impurity in the solution, a series of potassium dihydrogen phosphate (KDP) crystals was obtained by the conventional temperature cooling and the rapid growth methods, respectively. It was observed that the presence of SiO₃^2‐ made KDP crystals tapering in conventional cooling method, while more SiO₃^2‐ induced inclusions at prismatic sectors in the rapid growth method. Laser‐polarization‐interference results showed that SiO₃^2‐ extended the dead zone and reduced the growth rate of (100) face of KDP crystals. The negative influence of SiO₃^2‐on the growth was considered absolutely similar to the effect of cations. It was also suggested that the stability of solution doped with SiO₃^2‐ was improved without seed crystals, while it was destructed with seed crystals. The inhibition mechanism was analyzed in terms of SiO₃^2‐ absorption on (100) face. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simulating vapour growth morphology of crystalline urea using modified attachment energy model

We report a computational model to simulate vapour growth morphology of urea crystal by considering molecular anisotropy and surface relaxation of different crystal faces. It has been argued that the faces' growth occurs through the adsorption of molecular layers rather than a slice of thickness d_hkl. The molecular layer is a 2-D periodic arrangement of molecules in which each molecule has same the orientation. The molecular orientations in a slice of thickness d_hkl may differ from each other and depend on crystallographic orientation of the slice. The discussed approach has been employed to simulate vapour growth shape of crystalline urea by calculating attachment energy of molecular layers using Hartee–Fock and density functional theories. The calculated growth morphology is in good agreement with the vapour grown shape of urea crystal. The role of thermal and growth kinetics affecting the vapour growth morphology has been discussed. The observed polar growth morphology of urea crystal has also been discussed particularly in the context of different atomic environments of (111) and (?1?1?1) faces.     

A Polymorph Crystal Structure of Hexaphenyl Observed in Thin Films

Highly oriented thin films of hexaphenyl — which are used in organic opto‐electronic applications — are characterised in terms of their crystal structures. Two different crystal structures of hexaphenyl (C₃₆H₂₆) are observed when the films are prepared by physical vapour deposition at various substrate temperatures. If the substrate is kept at room temperature, hexaphenyl crystallises within a structure which is already known from single crystal investigations. However, when the thin films are grown at a substrate temperature of 160°C a new crystalline phase appears. This structure was characterised by X‐ray and transmission electron diffraction. Due to the strong preferred orientation of the crystallites within the thin films, the lattice constants as well as main features of the new crystal structure could be determined. The lattice is indexed as monoclinic with: a = 7.98Å, b = 5.54Å, c = 27.64Å and β = 99.8°. The new crystal structure has high similarity to the already known crystal structure: Both structures are built by layers of hexaphenyl molecules, within one layer the aromatic planes of the hexaphenyl molecules are packed in a herringbone pattern. The characteristic feature of the new structure is that the long axes of the hexaphenyl molecules are arranged absolutely perpendicular to the layers, whereas, within the already known structure the long axes show an tilt angle of 17° to the layer normal direction.     

KDP single crystal growth via three‐dimensional motion growth method

A novel system for rapid crystal growth, namely three‐dimensional motion growth method (“3D MGM”) was proposed. Using this system, a potassium dihydrogen phosphate (KDP) seed was grown to a single crystal with a final size of 50×55×85 mm³. The KDP crystal was characterized by Raman spectroscopy, UV‐vis‐NIR spectroscopy, extinction ratio, laser damage threshold, and etching studies. Raman spectrum shows KDP crystal grown by “3D MGM” maintains good crystallinity as that grown by rotating‐crystal method (“RCM”). The “3D MGM” grown KDP crystal has much better transmittance, higher extinction ratio, higher damage threshold and less dislocation density, compared to “RCM” grown crystal.     

Growth defects in a PZNT93/7 crystal prepared by directional solidification

Novel relaxor ferroelectric crystal 0.93Pb(Zn_1/3Nb_2/3)O₃‐0.07PbTiO₃ (PZNT93/7) with dimensions about Ø40× 70 mm³ was obtained by directional solidification technique. The growth defects of the crystal were investigated. Rocking curve analysis revealed the crystalline quality of PZNT93/7 crystal was not perfect and the FWHM value was measured to be about 0.7°. Some pits and oxide particles in micro‐size were formed in the crystal due to the growth conditions. A series of growth steps parallel to (001) face were observed which were attributed to the growth behavior. Moreover, it was found the average chemical composition of the crystal was deviated slightly to the stoichiometric value of PZNT93/7. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)