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GEOLOGY AND MINERALOGY RESEARCH DEVELOPMENTS

CRYSTALS AND CRYSTAL
GROWTH

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GEOLOGY AND MINERALOGY
RESEARCH DEVELOPMENTS

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GEOLOGY AND MINERALOGY RESEARCH DEVELOPMENTS

CRYSTALS AND CRYSTAL
GROWTH

WILFRED CARTER
EDITOR

New York

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Crystals and crystal growth / Wilfred Carter, editor.
pages cm. -- (Geology and mineralogy research developments)
Includes index.
ISBN:  (eBook)
1. Crystals. 2. Crystal growth. 3. Crystallography. I. Carter, Wilfred, 1964- editor.
QD921.C865 2014
548--dc23
2014047568

Published by Nova Science Publishers, Inc. † New York

GeO2 Solid Solution for Piezoelectric Applications 1 Mythili Prakasam and Alain Largeteau Chapter 2 In-Situ Investigation of the Melt Structures in Borate Crystal Growth Systems 25 Songming Wan Chapter 3 Doped Organic Crystals with High Efficiency. Khaddour Index 93 www.ebook777.com .free ebooks ==> www.com CONTENTS Preface vii Chapter 1 Hydrothermal Crystal Growth from SiO2 .ebook777. Color-Tunable Emission toward Laser Application 53 Yang Zhao and Huan Wang Chapter 4 Modeling Effects of Impurities on Crystal Growth 71 Issam A.

Silicon oxide (SiO2) with α-quartz structure are the current frontrunners for piezoelectric applications due to its high electromechanical coupling co-efficient and Germanium Oxide (GeO2) is expected to be very interesting but the process to obtain large single crystal is yet to be realized. high frequency stability with frequency and time control circuits. helps in obtaining single crystals at medium temperature. its low melting point and high volatilization results in inhomogeneity in the grown crystals. Chapter 1 . radio frequency low pass filters for video and digital cameras. Wide field applications such as actuators. Due to lead (Pb) toxicity. The hydrothermal process is utilized for growing a wide variety of crystals.Hydrothermal crystal growth offers a complementary alternative to many of the classical techniques of crystal growth used to synthesize new materials and grow bulk crystals for specific applications. researchers worldwide are looking for an alternative.free ebooks ==> www.ebook777.ebook777. This specialized technique is often capable of growing crystals at temperatures well below their melting points and thus potentially offers routes to new phases or the growth of bulk crystals with less thermal strain. Though alkali niobates could be one of the viable candidates. The various parameters and their physico-chemical kinetic processes in obtaining crystals α-quartz of SiO2 and GeO2 by hydrothermal www.com PREFACE This book discusses several crystals and the crystal growth processes. Ti) O3] is widely used in piezoelectric materials in the limited temperature range (< 350oC).com . However with hydrothermal crystal growth. It is impossible to obtain large crystals of SiO2 and GeO2 by conventional crystal growth techniques. initiated research in quest of piezoelectric materials. Currently [Pb (Zr. where the crystal growth is carried out under sub/super critical conditions by varying temperature and pressure.

high doping ratio. and gave clear assignments of all important vibrational peaks in the melt Raman spectra. have been found in the Ba2Mg(B3O6)2 and BaB2O4 melts. However. and the lack of effective experimental techniques and theoretical analysis methods. as an effective theoretical method. High- temperature Raman spectroscopy is a powerful tool for the study of borate melt structures. Alkali-earth cations and [B3O6]3– rings. two polymer-like structural models have been proposed to describe the BiB3O6 and Li2B4O7 melt structures. verified the melt structural models. and good chemical and physical properties. Chapter 2 . They are related not only to the macro-properties of the melts. The density functional theory (DFT) calculation. .35: 23. but also to the micro- processes of the crystal growth. large size and excellent optical properties were prepared by physical vapor transport method.com viii Wilfred Carter crystal growth will be discussed in detail with a detailed literature review in this chapter. laser and luminescent materials due to their diversified structures. These doped crystals maintain the ordered layer structures and the crystal surface continuities.4-Distyrylbenzene (trans-DSB) crystals with high crystalline quality. An isomerization reaction between [B3O3Ø4]− (Ø = bridging oxygen atom) rings and [B3O4Ø2]– rings has been found in the CsB3O5 or LiB3O5 boundary layer.37) has been obtained by controlling an appropriate mol ratio of guest to host (tetracene: pentacene: trans-DSB= 1: 1.free ebooks ==> www. BiB3O6. A boundary layer in which the melt structure gradually changes to the crystal structure has been observed around the LiB3O5 or β-BaB2O4 (low-temperature phase BaB2O4) crystal−solution interface. The growth of high-quality borate crystals is required for their applications. CsB3O5. Efficient energy transfer from the host trans-DSB molecules to the guest molecules and the suppressing of the interaction among the guest molecules lead to color-tunable emission and high luminescent efficiencies. which are verified by X-ray diffraction (XRD) and atomic force microscopy (AFM) analysis.36.Borate crystals are widely used as nonlinear optical. as the structural units. and applied to understand the two crystal growth mechanisms and habits.ebook777. and has been applied to in-situ investigate the melt structures in the Ba2Mg(B3O6)2.Tetracene or pentacene -doped trans-1. Chapter 3 . LiB3O5. On the basis of the structural evolution around the growing BiB3O6 and Li2B4O7 crystals. A fundamental problem for borate crystal growth is the high-temperature melt structures in the crystal growth systems. the borate melt structures have been poorly understood because of the structural complexity. and Li2B4O7 crystal growth systems. Further. BaB2O4. the white-emission tetracene and pentacene -doped trans-DSB crystal with the CIE coordinate (0.1). 0.

ebook777. Chapter 4 . and discussed for the specific cases of sucrose grown from raffinose-doped solutions.com Preface ix The primary results of optically pumped laser experiment indicate that these crystals have the potential application for organic laser diodes. www. namely the birth and spread model. the size and the orientation of the impurity at the interface layer is reviewed. and deeply discussed.free ebooks ==> www. Finally. a hypothetical approach is presented to enable evaluating the effect of macromolecular additives on the occurrence of needle-like crystals. The concept of the impurity partition coefficient and its importance to the recrystallization processes is explained.This chapter represents specific review on the effects of impurities on the growth from solution. Furthermore. Further. Kubota-Mullin model as adsorption model describing the effect of the shape. benefiting of application of the 2D nucleation models.ebook777. to understand the effects of impurities on the kinetics and the interfacial free energy of growth is also illustrated.com .

Chapter 1 HYDROTHERMAL CRYSTAL GROWTH FROM SiO2 . Currently [Pb (Zr. Université de Bordeaux. Wide field applications such as actuators.cnrs. www.ebook777. 2] is widely used in piezoelectric materials in the limited temperature range (< 350oC). Due to lead (Pb) * Corresponding author: prakasam@icmcb-bordeaux. France Dedicated to Professor Gerard Demazeau on the occasion of his Lifetime Achievement Award in ISHA 2014 for his scientific contribution in high pressure research ABSTRACT Hydrothermal crystal growth offers a complementary alternative to many of the classical techniques of crystal growth used to synthesize new materials and grow bulk crystals for specific applications. high frequency stability with frequency and time control circuits. This specialized technique is often capable of growing crystals at temperatures well below their melting points and thus potentially offers routes to new phases or the growth of bulk crystals with less thermal strain. Ti) O3] [1. initiated research in quest of piezoelectric materials. radio frequency low pass filters for video and digital cameras. ICMCB.fr/ mythili.free ebooks ==> www. Inc.prakasam@gmail. Pessac.com.com .com In: Crystals and Crystal Growth ISBN: 978-1-63463-791-6 Editor: Wilfred Carter © 2015 Nova Science Publishers.ebook777.GeO2 SOLID SOLUTION FOR PIEZOELECTRIC APPLICATIONS Mythili Prakasam* and Alain Largeteau CNRS. The hydrothermal process is utilized for growing a wide variety of crystals.

Crystal growth under high pressure and high temperatures called as hydrothermal method is a solution growth where pressure improves the dissolution phenomenon. dissolving the solute components in liquid medium or flux is crystallized from supersaturated solutions by decreasing the temperature (at ambient pressures). In general crystal growth methods are classified into solution growth and melt growth techniques. liquid solid or vapor solid. the starting components are melted congruently and then solidified with a controlled cooling and pulling and/or rotation rate. These crystal growth methods are classified on the type of crystallization and one amongst them is the solution growth.com 2 Mythili Prakasam and Alain Largeteau toxicity. In solution growth. Bridgman-Stockbager and Verneuil methods. . Melt growth is divided into Czochralski. 1. Crystal growth is the result of phase transformations involving solid solid. Under melt growth techniques the material is subjected to very high temperatures in order to melt. Solution growth can be classified into low temperature solution growth and high temperature solution growth. INTRODUCTION Long range atomic order with repetitive structure gives rise to crystalline form. which could lead the formed product to be amorphous rather than the single crystal. Though alkali niobates could be one of the viable candidates. It is impossible to obtain large crystals of SiO2 and GeO2 by conventional crystal growth techniques. helps in obtaining single crystals at medium temperature. In all the aforesaid techniques. Viscosity of melt is another important factor. The various parameters and their physico-chemical kinetic processes [3. its low melting point and high volatilization results in inhomogeneity in the grown crystals. where the crystal growth is carried out under sub/super critical conditions by varying temperature and pressure. which could be detrimental for the compounds that is prone to phase transitions and thermal stability or decomposition. researchers worldwide are looking for an alternative. However with hydrothermal crystal growth.ebook777.free ebooks ==> www. Silicon oxide (SiO2) with α-quartz structure are the current frontrunners for piezoelectric applications due to its high electromechanical coupling co-efficient and Germanium Oxide (GeO2) is expected to be very interesting but the process to obtain large single crystal is yet to be realized. 4] in obtaining crystals α-quartz of SiO2 and GeO2 by hydrothermal crystal growth will be discussed in detail with a detailed literature review in this chapter.

ebook777. many European mineralogists succeeded in employing hydrothermal technique to obtain minerals. This resulted in searching for new solvents other than water. arsenates. HISTORICAL ASPECTS OF HYDROTHERMAL CRYSTAL GROWTH Hydrothermal method gained popularity in the initial 19th century for the production of quartz single crystals. Hydrothermal method can be classified under medium temperature solution growth. Initially water was the only liquid that was considered for usage in the hydrothermal method. Various groups of materials such as phosphates. silicates and various organic/ bio materials have been obtained by hydrothermal technique.ebook777. carbides. The sealed vessel was heated to 350oC. titanates. which is primarily employed for the materials which has low solubility and undergoing various phase transitions at ambient pressure and even at high/low temperature. which lead to obtain crystals of dimensions ~ 15 mm over a period of 7 months. in practice there are some of the non-aqueous solutions that are used as solvents. Hydrothermal process also helps in obtaining new phases of chemical materials with chemical stability. germanates. which are called as Solvothermal method.free ebooks ==> www. 2.GeO2 Solid Solution … 3 The crystal growth under medium temperature under high pressure is done by means of hydrothermal method. During 18th century. nitrides. decomposition. A detailed explanation on the hydrothermal technique for crystal growth is discussed in the following section. which resulted in very small size crystals. owing to the inherent low solubility of the solute. oxides. The first work of crystal growth of α- quartz was carried out by Schafhault and Senarmont in the order of size microscopic. G. which dissolves the solute particles and is capable of precipitating the dissolved solute particles with a temperature gradient which is impossible to obtain under ambient pressure and temperatures. The origin of the term Hydrothermal originates from the usage of aqueous solution as solvent.com Hydrothermal Crystal Growth from SiO2 . vanadates. sulfides.com . fabrication of nanoparticles with defined size and morphology. Conventionally hydrothermal method is used to initiate heterogeneous chemical reactions(between solid and liquid phases) in the presence of aqueous solvents under high pressure at medium temperature. tungstates. Spezia [5] developed a crystal growth technique during 1898 and 1908 with a sealed vessel by incorporating the solution of sodium silicate and natural quartz. corrosion and etching of the materials are reported. However. fluorides. hence the www.

Various applications such as piezoelectric. Benefits of hydrothermal processing also include powder preparation (non-agglomerated. HYDRODYNAMIC ASPECTS OF HYDROTHERMAL CRYSTAL GROWTH The basic aspects that are considered during hydrothermal growth are (1) Wide range of temperature and pressure conditions for various aqueous solutions and their physico-chemical studies are studied. temperature and various chemical components in the formation of the chemical components. which could undergo thermal decomposition at high temperatures to obtain dense or porous material with distinct microstructures. Hydrothermal method [6-9] is preferred and is advantageous over other conventional crystal growth techniques due to the following 1. controlled morphology) and reactive sintering to obtain new phases at comparatively low temperatures and high pressures.quartz crystal growth is well developed and is industrialized in various countries across the globe. optical. Stabilization of required oxidation states for the metal compounds 3.ebook777. Syntheses of the metastable compounds 2. Currently the technology of α. magnetic and biomedical require large defect free crystals that are usually grown by hydrothermal method. Helpful in obtaining the compounds which undergo low temperature phase transitions As all the reaction kinetics takes place in the closed system at various pressure and temperature (subcritical and supercritical condition). Hydrothermal crystal growth is preferred generally to obtain large and defect free single crystals (mostly the materials that present structural transitions).com 4 Mythili Prakasam and Alain Largeteau hydrothermal process was invented. it is possible to define the influence of pressure. The difficulty to obtain natural quartz for piezoelectrical applications during the second world war lead to the active research for looking into alternative methods to obtain single crystals of Quartz. Hydrothermal sintering involves the processing of organic/ inorganic compounds.free ebooks ==> www. 3. (2) Effect of the temperature and pressure to yield the single crystals by hydrothermal method .

hence the hydrothermal conditions are different for different kind of compounds. Deviations from Raoult‘s law takes place when there is a strong interaction between the solute and the solvents. kinetics and growth mechanisms of the single crystals can be studied by the aforesaid interactions. Regarding the growth of the single crystals by hydrothermal method either by homo/ hetero epitaxial techniques are carried out in the different ways such as (i) Dissolution of the required starting components (nutrient) in mono/ polyphasic components by convective mass in the dissolution zone transfer reaches in the growth zone and helps in interaction of the dissolved components to deposit the layer on the seed surface. final composition of the product. These interactions lead to acquiring knowledge on the influence of the solution components such as type of solvents. and solubility under a particular hydrothermal process.TΔS= RTlnK (1) Where K is equilibrium constant.free ebooks ==> www. where the solute transport or deposition occurs by convective mass transfer. Further solubility of various solutes change according to the solvent used. In addition.GeO2 Solid Solution … 5 Hydrothermal crystal growth experiments are usually carried in vessels with a gradient of temperature. www.com .com Hydrothermal Crystal Growth from SiO2 . when the transition from one solvent to another which is shown by the following equation ΔG= ΔH. influence of the starting component (nutrient). (ii) Recrystallization of the solute from the saturated solution under sub/supercritical conditions. It can be observed from equation 1 that the solubility influences the enthalpy and entropy of the system (at constant Pressure ―P‖ and Temperature ―T‖) is different for different solvents. The different aspects of solvents in hydrothermal system are discussed in the following section. their concentrations. The change in the thermodynamical system can be elucidated by the change in Gibb‘s free energy.ebook777.ebook777.

when 1M NaOH is prepared at room temperature. the molecular mobility increases due to the decrease in the solvent viscosity. But the solvent have to be chosen for each compound system based on its solubility and various physico-chemical aspects with changing temperature or pressure. dielectric constant. The solubility of nonpolar species increases in- contrast to the ionic and polar species which decreases as a result of the solvent polarity.ebook777. Further it is essential to know the absolute solubility of the crystallizing material and viscosity of the solvent which should have insignificant toxicity and inert with the internal wall of the autoclave (vessel). Potassium hydrogen phosphate (K2HPO4) etc. Consequently.. as we discussed above the supercritical water acts as a unique medium that accelerates the chemical process of the constituent solute system. The above phenomenon can be understood in terms of the thermodynamical and transport properties of supercritical water. Since solvent viscosity and diffusion are inversely proportional to each other. In hydrothermal process. In addition the . Large compressibility is obtained as a result of hot and less dense fluid. Hydrothermal solvent depend on viscosity. The higher growth rates can be expected if there is a narrow diffusion zone near the growth interface.. sodium carbonate (Na2CO3).free ebooks ==> www. This compressibility is an important factor that is used in the calculation of density change with pressure. For ex. Under the hydrothermal conditions. Ammonium Fluoride (NH4F). there are drastic changes that lead to ionic hydration. the solubility depends on the type of solvent at different P and T. the viscosity of the hydrothermal solutions reduces to about two orders of magnitude lower than that of ordinary solutions.com 6 Mythili Prakasam and Alain Largeteau 4. which reduces the dielectric constant and density. Under hydrothermal conditions. compressibility and co-efficient of expansion. it leads to rapid diffusion in hydrothermal growth which in turn gives rise to single crystals of well-defined morphology. Various mineralizers which help to amplify the dissolution effect such as sodium hydroxide (NaOH). drastic change in dielectric constant at high pressure and high temperature leads to complete dissociation of electrolyte at ambient temperatures and ambient pressure to be highly associated in the supercritical region. HYDROTHERMAL SOLVENT BEHAVIOUR The synthesis and recrystallization of various compounds and fabrication as single crystals on the seed depends on its chemical and physical properties. which is conversely different than the properties of water at ambient conditions. However. which will cause constitutional supercooling and gives rise to dendritic growth.

modified Bridgman and cone enclosure (high pressures). The supersaturation that is established in the hydrothermal system is dependent on the magnitude of the temperature gradient (ΔT) between the dissolution and growth zones.free ebooks ==> www. Hydrothermal crystal growth is done in a closed vessel under pressure called ―vessel‖.2oC) and critical pressure (Pc= 22. The vessel is divided into two zones: (a) dissolution zone and (b) growth zone.GeO2 Solid Solution … 7 role of thermal expansion co-efficient is indispensible as an important parameter that helps in obtaining defect free and strainless crystals by hydrothermal technique. CRYSTAL GROWTH BY HYDROTHERMAL Hydrothermal crystal growth method is more analogous to crystal growth from aqueous solution at ambient temperature. Based on the pressure that is desired in vessel different types of materials are chosen such as glass vessels (low pressures). steel vessels (medium pressures). If the material has positive solubility. and the seed is suspended in www. welded sealed vessel. 5. The growth rate increases linearly with supersaturation leading to deposition on each face of the seed.com Hydrothermal Crystal Growth from SiO2 . the rate increases sharply at low concentrations and remains practically unchanged at high concentrations and (ii) An increase in growth rate on the faces is observed with the increase in pressure which help to improve the dissolution of the nutrient. Co-efficient of expansion of water under hydrothermal conditions is large. then the charge (nutrient) material is placed in the bottom of the vessel (warm zone).1 MPa). which is believed to have played a significant role in the origin of life on earth. There are various reports that show the variation of water under ambient/high pressure and ambient/high temperature conditions. The schematic representation of hydrothermal method is shown in figure 1. Growth rate is determined by the ratio of increase of seed size and duration of the experiment run. Significant difference in the crystallization rate on each face shows the primary role of surface processes that take place at the crystal solution interface. Though pressure doesn‘t have any direct effect on the growth rate of the crystals.ebook777. it has significant influence on other parameters such as mass transfer and solubility. irrespective of the chemical constituents in the hydrothermal system. At the critical point. Crystallization rate can increase in two ways (i) With system that contains the solvent components. Supercritical water is obtained above critical temperature (Tc= 374. the phases of liquid and gas are not distinguishable.ebook777.com .

(cool zone) r. So the material constituting the vessel should have adaptable characteristics. Thermodynamical parameters such as P. When acmite is thick inside the vessel. This makes passivation cycle necessary before using autoclave for the crystal growth. Table 1.8M Crystal growth rate 1 mm/day 0. the nutrient is at the top (cool zone) and the seed is at the bottom of the vessel (warm zone). The vessel is heated in order to obtain the required temperature gradient. which is very difficult to remove when once formed. temperature and aggressive fluids over a long period of time. it will lead to problem for experiment processing. The required quantity of aqueous solution is filled in the vessel according to the pressure and temperature required following the thermodynamical conditions desired.free ebooks ==> www. The vessels are made to withstand the various constraints such as pressure. T and ΔT govern to determine the crystal growth rate in addition to the diaphragm opening and the type of solvent used.com 8 Mythili Prakasam and Alain Largeteau the top of the vessel. . else this layer becomes too thick. This temperature gradient helps in transporting the solute molecules from the warm zone to the cold zone by the convection process.4 mm/day This is mostly observed in case of α-quartz crystal growth in the form of thin layer of acmite (NaFeSi2O6) on the internal wall of vessel. It is well known that the steel is an alloy based on Iron ―Fe‖ which could react with the solute upon reaction with aggressive solvents. Most of the industrial vessels are made in steel. Table 1 shows the general conditions employed in industries for the growth of α-Quartz crystals. Thermodynamical parameters employed in industries for SiO2 single crystals Parameters High pressure Low pressure Temperature 360oC 345oC Pressure 150 MPa 70-100 MPa Gradient 25oC 10oC Solvent NaOH 1M Na2CO3 0. In the case of negative solubility of material. The vessels are constructed in such a way that is capable to work both at high and low pressures.ebook777.

F-. Figure 3 shows the phase diagram of SiO2. 109 o. The low temperature transition from -. Most oxygen atoms will be bonded to silicon atoms.GeO2 Solid Solution … 9 6. -Cristobalite has advantages such as availability in high purity state and can be prepared with relative ease of particles with uniform size. where as a large increase in molarity gives rise to additional chemical phases which could deposit at the bottom of vessel that inhibits the solute to be transported to the crystal growth zone. α-Quartz crystal structure can be defined as tetrahedral arrangement with silicon surrounded by four oxygen atoms (Figure 2 (a)).com Hydrothermal Crystal Growth from SiO2 . Each crystalline form of quartz. Furthermore. Cl-. but the solubility could be markedly increased by the addition of OH-.ebook777. The bond angle Si-O-Si is nominally about 145o. (0. metastable tridymite and metastable cristobalite consists of high and low temperature structural forms called as  and .and acid media. -QUARTZ –GENERAL PROPERTIES AND APPLICATIONS SiO2 is found both in crystalline and amorphous form in nature.61 Å.I. The high temperature crystal growth techniques cause cracks on the surface of the crystals which is due to the phase transitions during cooling. respectively. A slight increase in molarity can accelerate the growth rate of the crystal. Tridymite and Cristobalite. makes the fabrication of -Quartz crystals impossible by conventional crystal techniques. rotation of the bond about the axis is almost completely free (Figure 2(b)). but can vary from about 100 to 170o with very little change in bond energy. There are about 22 polymorphic modifications with three principal crystalline forms of SiO2 such as Quartz. The solubility of quartz in pure water is found to be low for crystal growth (~ 0.1- 0.3 wt %). so that two tetrahedral are joined at a corner. the Si-O distance is 1. Hence hydrothermal crystal growth method is considered to be an apt technique to grow these crystals. High temperature forms of cristobalite and Tridymite can exist in metastable state below its transition temperature. Br-.ebook777.free ebooks ==> www.com . It is the oxygen bonds between silicon atoms that give SiO2 many of its unique properties. The www. -Cristobalite is a polymorphic form of silica which has higher solubility than quartz. -Quartz is stable up to 573oC and is widely used for various technological applications such as piezoelectrics. The bond angles around O-Si-O are essentially the tetrahedral angle. Each silicon atoms are bonded to 4 oxygen atoms.16 nm) with very little variation. The stability of each of the structural forms of Quartz is different and well defined under equilibrium conditions.

ebook777. . Crystal structure of α-quartz SiO2 and bond rotation angles in α-quartz SiO2. Figure 2.com 10 Mythili Prakasam and Alain Largeteau minimum molarity that has been studied to result in good growth rate is about 0. Figure 1.25 M NaOH.free ebooks ==> www. Schematic representation of hydrothermal crystal growth.

cracks or air bubbles significantly reduces the Q-factor. Presence of the defects in quartz crystals alters the device properties to a greater extent. With its high Q- factor at resonance and low manufacturing costs in addition to the aforesaid properties made Quartz as one of the principal material in employing in frequency controlling devices in electronic equipment. Fluctuations in the thermodynamical parameters governing the crystal growth and inclusions of foreign particles lead to structural defects in Quartz. GeO2 is also often related to its structure of oxides such as Borates (B2O3) other than SiO2.free ebooks ==> www. Figure 4 shows the various applications of quartz in devices. But it has to be noted that the phase diagram of GeO2 has comparatively lesser number of structural polymorphs in comparison to SiO2. With the help of optimizing the crystal growth parameters it is possible to avoid the defects that are observed in the natural crystals (in terms of composition and structure). the resulting changes occur at a comparatively lower pressure than their SiO2 counterparts. Further variation in the size of Ge in comparison to Si and their relative bond lengths and bond angles are obvious. Presence of any defects such as impurities. Additional benefits of growing the crystals by hydrothermal method is that the crystal grows under less thermal strain and therefore it is possible to control the stoichiometry by producing in the oxidizing or reducing conditions by using some chemicals additive. The crystalline. 7. The defects are also induced from the chemical corrosion caused on the internal wall of vessel depending on the solvent and the metal of the vessel. www.GeO2 Solid Solution … 11 -Quartz is one of the stable materials used in electronics industry due to its high chemical stability. piezoelectricity and high mechanical strength. Most of the defects induced in the grown crystals also depend on the nutrient used or solvent used.com Hydrothermal Crystal Growth from SiO2 . Quartz is also widely known to be a piezoelectric material which exhibit electric charge upon subjecting to pressure. Crystalline quartz with its low temperature co-efficient will lead to a small change in resonant frequency with any difference in temperature with high Q factor at resonance.com .ebook777.ebook777. glassy and liquid phases of GeO2 when subjected to high pressures. GERMANIUM OXIDE (GEO2) CRYSTAL STRUCTURE Germanium oxide [10-12] is an analogue of silicon oxide structurally and chemically.

Phase diagram of SiO2. Figure 4. .ebook777.free ebooks ==> www.com 12 Mythili Prakasam and Alain Largeteau Figure 3. Few examples of Quartz crystal applications.

com Hydrothermal Crystal Growth from SiO2 .com .ebook777. -quartz like structure of GeO2 has been demonstrated to exhibit stability at high temperature. Structural difference essentially leads to the difference in the behavior of - quartz SiO2 and GeO2 under high pressure. sensors and oscillators. Na. black. The aforesaid devices require quartz single crystals of very high quality. microwave wafers. The aforesaid can be verified from the transformation of -quartz to the high pressure Rutile structure results at 10 GPa. Brazil and Madagascar. but the -quartz like structure of GeO2 occurs at 2 GPa. defectless and transparent. These types of colored quartz crystals are prevalently used for ornamental purposes. Ti or Co. www. - quartz like structure of GeO2 undergoes the compression by tilting of the tetrahedral makes germanate structure to undergo the pressure induced transformations at lower pressure than the -quartz structure. Al. Natural Quartz is prevalently found in Russia. which arises from the rotation or tilting of the tetrahedral around the shared bridging oxygen. 8. piezoresonators. The quartz crystals of average quality are mostly used for fabrication of watch and ornaments. Natural quartz have coloration such as brown. SIO2-GEO2BASED SINGLE CRYSTALS BY HYDROTHERMAL METHOD -Quartz is the stable form of SiO2 under the normal conditions of pressure and temperature. Excellent crystal quality and its associated piezoelectric properties with little cost of fabrication make -Quartz one of the widely used materials for application in piezoelectrics.GeO2 Solid Solution … 13 Crystalline GeO2 has two structural polymorphs. When the quartz crystals are colorless. and the crystals of high quality are used for spatial and military applications. In particular. H. The atomic bridging structure of -quartz GeO2 is shown in figure 5.ebook777. pink and yellow due to the presence of various impurities substituting Si4+ by atoms such as Li. which are extremely difficult to obtain naturally. such as -quartz like (P3221) trigonal (hexagonal) structure and Rutile type tetragonal (P42/mnm) structure. defect free and preferentially oriented. it present a great interest for wide variety of technological applications such as electronics. but with basic differences in the structure.free ebooks ==> www. Natural quartz is found in the volcanic rocks and sediments. blue.

Figure 6. Atomic bridging structure in GeO2. . Figure 7. Variation of electromechanical coupling coefficient with inter-tetrahedral bridging and tilt angle in SiO2.free ebooks ==> www. Phase diagram of SiO2-GeO2.com 14 Mythili Prakasam and Alain Largeteau Figure 5.ebook777.

com . Obtaining crystals of SiO2-GeO2 will not only help us to know the crystal chemistry but also to improve the piezoelectric properties by adjusting the concentration of Germanium in the lattice of quartz.ebook777. Sn4+. Further due to the difference in the solubility limit of SiO2 and GeO2. substitution occurs also when the charge is different. The dopant in the quartz seems to enter the lattice either by substituting or in interstitial position.GeO2 Solid Solution … 15 Miller et al. In the family of materials such as XO2 (X= Si. On the other hand. Solubility of Quartz in water is low. then the lattice of SiO2 cannot accommodate Ge with co-ordination number 6 in thermodynamic conditions because the domain is biphasic. Ga. As5+. hence mineralizers such as NaOH leads to the impurities such as sodium in the crystal.1 changes the transition temperature of α  of Quartz from 573oC to 660oC. [13] was the first to report on the phase diagram of SiO2 and GeO2 solid solutions (Figure 6). there are very few details on the growth of SiO2-GeO2 solid solution systems. Li+.free ebooks ==> www. which makes it even more complicated to know about the problems arising due to the inhomogeneity of the composition. It has been verified by thermal analyses that the addition of germanium even in minute quantities such as 0. to date no structural refinement of the SiO2-GeO2 has been reported. The solid solutions of different compositions were obtained by hydrothermal recrystallization with SiO2 and GeO2 precursors in sealed capsules at 700 bars. Al. Germanium appears in the form of rutile with co-ordination number 6.com Hydrothermal Crystal Growth from SiO2 . In contrast to the well developed crystal growth technique of quartz. The conventional reflux technique used for the growth of GeO2 cannot be employed due to the poor solubility of SiO2 under these conditions. traditionally used crystal growth method of quartz which necessitates the use of mineralizer will reduce the possible content incorporation of Ge in the SiO2 matrix. In addition. The ions such as Ge4+. Ge) and MPO4 (M= Fe. which is composed of either only XO4 corner shared tetrahedral or both of MO4 and PO4 tetrahedra forming a trigonal system. Quartz lattice is vulnerable to the substitution of ions which are similar to Si4+ in terms of ionic radii and valence state. B) family with -quartz analogue. Sometimes. Impurities can also enter the interstitially paving way to accommodate large ions to be placed in its structure. B3+. Ag+ and Zr4+ can be added to incorporate in quartz.ebook777. Pb2+. If > 31% wt. Ti4+. it makes the growth of these crystals very delicate and complicated by the hydrothermal method. Previous research works have confirmed experimentally that the large piezoelectric properties of -GaPO4 and -GeO2 materials in comparison to - www. Al3+. The maximum miscibility of germanium in the quartz lattice was found to be 31 % wt at 700oC.

ebook777. . The aforesaid materials are directly related to their structural distortion with respect to the . The general procedure for the single crystal growth by hydrothermal method. Natural GeO2 is known to be more stable in rutile structure than in the trigonal structure.free ebooks ==> www. Similarly - phase transition doesn‘t occur in -GeO2 and -GaPO4 Crystals. Under normal atmospheric pressure. GeO2 exhibits two forms of differing anion coordination around the central cation of -Quartz type with trigonal structure and rutile type modification in Tetragonal structure. - phase transition which appears around 573oC in -SiO2 [=144.2o] does not occur when the tilt angle  is over 22o (leading to  under 136o] (Figure 7). GeO2 is in stable trigonal phase from 1033oC upto the melting point at 1116oC.com 16 Mythili Prakasam and Alain Largeteau SiO2. the transformation from the rutile-like form to -Quartz type has been reported to occur in the temperature range of 1024-1045oC. Figure 8. GeO2 crystals grown by hydrothermal method contains high OH inclusions which easily transforms into rutile like structure upon heating upto180oC.Quartz structure type. -FePO4 and -AlPO4 compounds [14].

INCONEL is highly resistive in the base medium.5% atomic) type of alloy is also used. because of the formation of sodium germanate. Though the gasket is sensible to scratches. The cone type of gaskets are scratch resistant whereas Bridgman type of gaskets are delicate to operate. Perigny France.15% and Fe. It has been reported that Si0. INCONEL 625 (Ni-58%. There are security pressure leakage valves to open up on increase of pressure.GeO2 Solid Solution … 17 Conditions for device fabrication of -Quartz SiO2 can also be considered valid for -Quartz GeO2 for piezoelectric applications.com Hydrothermal Crystal Growth from SiO2 . Mo-8%. The pressure and temperature are measured with the help of thermocouples and pressure sensors. slot for thermocouple passage and evacuation tube. Design of the vessel geometry also plays a vital role in obtaining the temperature gradient. The 8 screws on top help the obturator to force it up and secure the gasket to be leak proof. To be leak proof. Any problem with this closing system will lead to leakage. By integrating the computer programming with Eurotherm monitors. this system is beneficial as more the pressure is increased more secure are the gaskets. Ta. such as cone type gaskets and Bridgman type gaskets. At ICMCB.com . with high elastic constants and good stability of temperature. Cr-20%. The substitution of Ge atoms in -Quartz SiO2 is believed to accentuate the piezoelectric properties and thermal stability of -Quartz SiO2.free ebooks ==> www. The aforesaid are the prime places that lead to the leakage. but has all the characteristics that are beneficial for quartz type crystal growth. This alloy is based on nickel with very minimum content of Fe.07O2 has high piezoelectric co-efficient in comparison to SiO2 [12]. One of the possibilities to incorporate the higher germanium content in -Quartz crystals of SiO2 is by processing the crystal growth experiment at high pressure > 2500 bar and temperatures until 700oC with dilute aqueous alkaline or fluorides solutions.3. www. However these conditions doesn‘t apply for Si1-xGexO2 (SGO).93Ge0. Hydrothermal quartz crystals are generally grown with NaOH (1M) and Na2CO3 (0. It can be inferred from the phase diagram of SiO2-GeO2 that the maximum content of GeO2 that can form single phase is 31 at % at about 700oC and 70 MPa under hydrothermal conditions.ebook777. Other key points are windings for closing the vessel. the temperature is programmed and monitored with the help of Labview. The single crystals of SGO with the -Quartz type structure is obtained by using Nichrome alloy or stainless steel vessels. The aforesaid conditions are inappropriate to be employed to obtain large dimensions.ebook777. various types of joints are used. In order to avoid this problem. hydrothermal crystal growth is carried out in the machine designed by M/S HPSystems. Co. extreme precaution should be taken.8M) at about 150 MPa and 360oC.

the nutrient dissolves and saturates the . The surface of the seed is cleaned with HF at 70oC. such as amorphous. and then thermally heated either to form amorphous phase or cristobalite form (Figure 11) in conventional furnace.com 18 Mythili Prakasam and Alain Largeteau Figure 9 shows the vessel and the basket for nutrient with 2 seed crystals attached that is used before the experiments. The preparation of the nutrient for germanium oxide with silicon oxide requires pre-preparation. When the temperature is high enough to initiate crystal growth.free ebooks ==> www. The pressure inside the vessel can be varied with the content of solvent and nutrient that also regulates the temperature difference between the crystal growth and dissolution zone. solid and powder form. Due to the variation of the solubility and solubility kinetics of GeO2 and SiO2. In order to avoid the aforesaid problems.ebook777.Quartz GeO2 is available in the form of powder. The quantity of the water to be filled and the pressure reached in the vessel can be determined by Kennedy‘s curve (Figure 10 (a)). Usually SiO2 is available commercially in three forms. α-Quartz SiO2 analogue of α. SGO nutrient is taken in the basket. results in very low solubility of GeO2. The amount of nutrient in the basket determines the size of the crystal to be grown. The seeds are suspended on the rod supported with the nutrient carrying basket. Figure 9. SiO2 and GeO2 are mixed in the desired ratio. A baffle separates the two zones in order to facilitate the growth of crystals with uniform dimensions in the crystallizing zone. Further the transformation of the rutile form GeO2 under hydrothermal conditions in pure water above 180oC. the resulting crystals may be non-stoichiometric. Synthetic quartz oriented perpendicular to the Z-axis of the crystal is used as the seed (Figure 10 (b)). (a) Top view of vessel INCONEL and (b) Basket containing nutrient with seed α-quartz crystal attached.

The nutrient required for continuous growth is obtained by convection currents caused by the temperature gradient. Figure 10. Hydrothermal crystal growth in the vessel is dependent on the supersaturation conditions in the cool zone and crystal growth rate. The starting materials will be dissolved directly in the growth vessel. The deposition from the supersaturated solution causes the growth of crystal on the seed. A small perforation in the basket allows also the thermocouple to pass through until the bottom of vessel. which in turn is dependent on the kinetics between the starting compounds i. hence the nutrient is taken in the basket. Quartz crystals are grown on the seeds of oriented - quartz single crystals SiO2. The starting nutrient compounds based on SiO2 and GeO2 varies primarily into two principal groups such as crystalline phase with cristobalite www.com Hydrothermal Crystal Growth from SiO2 . The temperature and the pressure in the vessel are recorded with the help of thermocouple and pressure sensor. which are prepared by cleaning the surface of the seeds with HF/ NaOH. The vessel is cold in the top which results in supersaturation of the solution. which will be introduced in the vessel.e.ebook777. (a) Kennedy‘s curve and (b) Z-oriented seed of Quartz crystal. The baffle regulates the transport of the growth species from the saturated solution (warm zone) to the growth zone (cool zone).free ebooks ==> www. SiO2 and GeO2. The basket facilitates to hold the nutrient and at the same time it avoids the easy management of charge to be removed after the experiment..com .GeO2 Solid Solution … 19 solution.ebook777. The temperature ranges from 300oC to 500oC and the pressure ranges from 100 MPa to 300 MPa to grow the quartz single crystals with a temperature gradient between 5oC to 100oC. This process is continuous and leads to the growth of large crystals.

which will decrease the quantity of Ge in the crystal grown. the thermodynamical conditions should be varied in order to forcibly dissolve the nutrients. When pure water is used as the solvent. In the aforesaid case. the content of Ge is high. In some cases. Formation of Na4Ge9O20 phases in the residual nutrient is observed at the end of the crystal growth. but it decreases the growth rate. there are cracks observed inside the seed used in pure SiO2 due to the high stress by the structural difference between the SGO crystal and SiO2 seed interface.2M. However the concentration of NaOH <0. On the other hand. France. when the quantity of NaOH increases the growth decreases. but the distribution is less homogeneous. The transport of species can be judged by the temperature gradient in the vessel. which is capable of working until 3500 bar. The high solubility of Ge in water is one of the prime reasons for which the composition of the grown crystal can be not similar as that of the nutrient.ebook777. Figure 11.free ebooks ==> www. High pressure crystal growth experiments to obtain SGO crystals were carried out in the vessel designed and developed by M/S HPSystems. the growth rate of quartz increases.20) Crystal growth experiments of SGO. when done with NaOH. high temperatures T> 400oC and P > 200 MPa is required. Nutrient preparation in SiO2 sintered crucible for SiO2-GeO2 solid solutions. the increase of Ge content in Si1-xGexO2 increases the germanium species in the pure water as solvent. 450oC with vessel capacity . homogeneous distribution of Germanium is reported when the temperature is less than 415oC.com 20 Mythili Prakasam and Alain Largeteau type structure with composition Si1-xGexO2 (x=0. Further with the increase of Ge content. In this case. A small gradient allows the transport of species in a very controlled manner and it increases the crystalline quality.

(a) The three zones furnace with adjustable refractory element and (b) Gasket and 8 screw (obturator). Bulk crystals of SGO (t=4 mm) were obtained after a period of 2 months.com Hydrothermal Crystal Growth from SiO2 .com .free ebooks ==> www. Figure 12. which is shown in Figure 14. Figures 12 and 13 shows the various components of the hydrothermal equipment used at ICMCB for growth of SGO crystals. Figure 13. (a) Top view of high pressure system (top heat protecting system open) and High pressure security valve/regulation part and (b) Complete view of hydrothermal system interfaced with computer.ebook777. Electron probe microscope analysis has confirmed the presence of Ge in the lattice of SGO.5 l.GeO2 Solid Solution … 21 of 1.ebook777. www.

A. 92.ebook777. Bruce. Appl. Mannur. (2008). XiaoningJiang. Ltrs.503.. In order to construct the devices. By substituting ―Si‖ ions with ―Ge‖ is a way to increase the piezoelectricity. [2] Mark. . &Demazeau.. Chai.G. Due to the phase transitions. Jason McMichael. EPMA of the grown SGO single crystals by hydrothermal method. Goglio. Journal of Intelligent Material systems and structures. Darraq. YitingFei. Eric Frantz. In order to grow the SiO2 doped with GeO2. High Pressure Research.14. and Thomas R. Robert Sadlerand Bill Nagel. & David W. CONCLUSION Quartz crystals are currently well known for their remarkable properties such as piezoelectricity. S. [3] Largeteau. G.& Schulz. Various aspects of hydrothermal crystal growth have been discussed in terms of solvents and instrumentation in detail. REFERENCES [1] Shujun Zhang. Further high pressure helps in conjunction with other parameters such as temperature gradient helps in obtaining SiO2 doped with Ge. 693. (2008). large defect free single crystals are needed. David Clayton.free ebooks ==> www.com 22 Mythili Prakasam and Alain Largeteau Figure 14. J. T. hydrothermal crystal growth technique is one of the best methods to obtain large size crystals with Z parallel faces for piezoelectric properties. Phys. Sundaresan. (2003). it is necessary to prepare the cristobalite nutrient to obtain homogeneous composition. J. 202905. H. 28(4). Snyder. Shrout.

S. A. Cryst. J.48.V.com .. Laudise. Masahiro Yoshimura. 13. G. Haines. S. www. Phillippot. &Papet. (1985).&Yu. Cambon.(1975).ebook777. Am. 36.K. 4220. [9] Byrappa. C. M. Menaert. A.. 1. Chem. M. Debray. Pintard. C. [6] Robert. 407. Palmier.S. (2001)..50. W. Darracq. D. Cambon. Handbook of Hydrothermal TechnologyNorwich. Encyclopedia of Applied Physics. A.(2013). Reviews of Modem Physics. E. B. (1905). 40. [13] Miller. A. H. (2000). (1963).. R. Dorner. P. [11] Yu.. Chemical And Engineering News. [7] Brice. 15. E.. Mineral. V.. 65(39) 30.. (1996). V. P.254. D. (2011). 365. Phys. Armand...free ebooks ==> www. E. Roy. J.. 57 (1)... Growth Des. [10] Lignie. Dachille. J. Inorg. Silvestrova. Balitsky.com Hydrothermal Crystal Growth from SiO2 .ebook777. New York: Noyes Publications. (1996) Journal of Solid State Chemistry.GeO2 Solid Solution … 23 [4] Ranieri. Balitsky. 123. Pisarevsky. Proceedings of the Royal Academy of Sciences in Turin. B..1024. Pisharovsky.. F. Solids. 177.&Shafer. [5] Giorgio Spezia. 105... Pena. J. O.. Largeteau. (1987). V. O. [14] Philippot. Yu. Goiffon. 4632. [8] Gary Johnson and Jonathan Foise.. Chem. &Demazeau. IEEE/EIA International Frequency Control Symposium and Exhibition. D. [12] Grimm. A.

have been found in the Ba2Mg(B3O6)2 and BaB2O4 melts. laser and luminescent materials due to their diversified structures.com In: Crystals and Crystal Growth ISBN: 978-1-63463-791-6 Editor: Wilfred Carter © 2015 Nova Science Publishers. and has been applied to in-situ investigate the melt structures in the Ba2Mg(B3O6)2.com .ebook777. R.ebook777. BiB3O6. the borate melt structures have been poorly understood because of the structural complexity. as the structural units.free ebooks ==> www. Chapter 2 IN-SITU INVESTIGATION OF THE MELT STRUCTURES IN BORATE CRYSTAL GROWTH SYSTEMS Songming Wan Anhui Key Laboratory for Photonic Devices and Materials. Inc. Anhui Institute of Optics and Fine Mechanics. High-temperature Raman spectroscopy is a powerful tool for the study of borate melt structures. However. A fundamental problem for borate crystal growth is the high-temperature melt structures in the crystal growth systems. BaB2O4. They are related not only to the macro-properties of the melts. China ABSTRACT Borate crystals are widely used as nonlinear optical. CsB3O5. and Li2B4O7 crystal growth systems. Chinese Academy of Sciences. and good chemical and physical properties. Alkali-earth cations and [B3O6]3– rings. and the lack of effective experimental techniques and theoretical analysis methods. The growth of high-quality borate crystals is required for their applications. A boundary layer in www. LiB3O5. but also to the micro-processes of the crystal growth. Hefei. P.

and three- dimensional networks [1]. sheets. the triangular and/or tetrahedral boron−oxygen moieties can further polymerize by sharing common oxygen atoms to form larger borate clusters. almost all borate crystals are grown from high-temperature melts (or solutions) with the transformation from the melt (or solution) structures to the crystal structures. 1. An isomerization reaction between [B3O3Ø4]− (Ø = bridging oxygen atom) rings and [B3O4Ø2]– rings has been found in the CsB3O5 or LiB3O5 boundary layer. as an effective theoretical method. surface and bulk acoustic wave devices [10]. As we know. The above-mentioned difficulties incent us to study the basic problems related to the growth of borate crystals in order to find the optimized methods to solve these difficulties.free ebooks ==> www. and neutron detecting materials [11]. (2) The incongruent melting character of some borate crystals.100 anhydrous borate crystals have been found and structural determined [2]. the problem of reproducible growth of large and high- quality borate crystals is far from being solved. However. The density functional theory (DFT) calculation. INTRODUCTION Anhydrous borate crystals are characterized by their structural diversity since boron combines with oxygen not only in three-fold (triangular) but also in four-fold (tetrahedral) coordination. and applied to understand the two crystal growth mechanisms and habits. Their growth generally relies on a very time-consuming trial-and-error method to determine suitable fluxes. The knowledge of the melt (or solution) . laser hosts [7–9]. more than 1. and gave clear assignments of all important vibrational peaks in the melt Raman spectra.ebook777. two polymer-like structural models have been proposed to describe the BiB3O6 and Li2B4O7 melt structures. On the basis of the structural evolution around the growing BiB3O6 and Li2B4O7 crystals. quite a few of them are used as nonlinear optical (NLO) [3] and birefringent devices [4–6]. Enormous efforts have been made in the past three decades to grow borate crystals [12]. The primary difficulties include: (1) The high viscosity of borate melts possibly due to their tendency to form various complicated structures. Up to now. such as chains. verified the melt structural models.com 26 Songming Wan which the melt structure gradually changes to the crystal structure has been observed around the LiB3O5 or β-BaB2O4 (low-temperature phase BaB2O4) crystal−solution interface. which limits mass transport and then leads to inclusions and voids heavily concentrated in the crystal boules.

and surface tension. the melt structure is the intrinsic factor to govern the melt macro-properties.ebook777. www.com In-Situ Investigation of the Melt Structures … 27 structures is of highest priority for the investigation of the borate crystal growth mechanism which is related to a variety of crystal growth phenomena and the formation of various crystal defects. investigators predominantly used borate glasses as the proxies for the borate melts based on the conjecture that a glass structure is closely analogous to the melt structure from which it was quenched [13]. boundary layer and bulk melt in a high-temperature crystal growth system. HIGH-TEMPERATURE RAMAN SPECTROSCOPY As compared with borate crystal structures that can be determined by X- ray or neutron diffractive method. However. Figure 1. In order to avoid experimental difficulties associated with high-temperature conditions. 2. However. such as viscosity. Both of the processes will influence the glass structure [14]. this method is still debatable because a glass structure only represents the super-cooled melt structure that has undergone a cooling and a glass transition process before the melt transforms to the glass. density. therefore. the borate melt structures have not been solved very well. which often determine the crystal growth conditions.com . Moreover. an accurate description of a melt structure requires in-situ experimental techniques. Crystal. an accurate structural description of a borate melt is very difficult not only due to the lack of experimental techniques but also the limitation of theoretical methods.free ebooks ==> www.ebook777.

when light traverses a transparent material. He found that. Raman spectroscopy is based on the Raman scattering phenomenon that was first observed experimentally in 1928 by C. the investigation of the melt structures in borate crystal growth systems demands the experimental technique being capable of micro-scale analysis. The spectrum contains the vibrational information of a molecule (or crystal lattice) and constitutes a fingerprint by which the molecular (or crystal lattice) structure can be identified. As a result. an Indian physicist who received the Nobel Prize in 1930 [24]. some of the deflected (scattered) light changes in wavelength. we call it boundary layer (see Figure 1). a transition region of melt structure should exist near the interface [15–17]. Raman spectroscopy is a well-established tool for molecular (or crystal lattice) structure analysis. V. Raman. including high-temperature X-ray diffraction [18].ebook777.free ebooks ==> www. Compared with other popular high-temperature in-situ experimental techniques.com 28 Songming Wan Moreover. However. The melt structure adjacent to the interface is under the influence of the well-ordered atomic potential of the interface. and the key to deduce the bulk melt structure. Raman scattering is inherently a weak process. Besides. high-temperature Raman spectroscopy combines the advantages of high- temperature. Generally. Today. a crystal growth process takes place near a crystal−melt interface. which further requires the in-situ experimental techniques having the ability of micro-scale analysis to investigate the melt structure in the boundary layer. X-ray photoelectron diffraction [20]. in-situ. and micro-scale analysis. However. The introduction of laser radiation sources has revolutionized this spectroscopic technique [25]. The Raman spectrum is represented by the intensity of the scattered light as a function of the frequency shift between the incident and scattered light. and thus very suitable for the melt structure study. and high resolution transmission electron microscopy [22]. neutron diffraction [19]. neutron diffraction. The melt structure in the boundary layer is essential to understand the crystal growth mechanism and other interfacial transport phenomena. the boundary layer is less than 1mm in thickness. the high sensitivity of Raman spectroscopy must rely on sufficiently intense radiation sources. Such a boundary layer has been supported by an increasing number of experimental results. and nuclear magnetic resonance techniques [23]. more sensitive to hyperfine structures than X-ray diffraction. high-temperature Raman spectroscopy is more convenient than high resolution transmission electron microscopy. nuclear magnetic resonance [21]. most of Raman spectroscopic studies are limited to room temperature because the high- . especially for which of the boundary layer. As we know.

(3) ultraviolet laser technique. and eliminate the influence of fluorescence [29].ebook777.free ebooks ==> www. More recently.com . which significantly decreases the photon counting of stray light. In order to eliminate the influence of the black-body radiation. as a new time resolution technique [28]. most stray light out of the optical focus is rejected. By using a confocal micro- Raman method. Meanwhile. the time required to record a Raman spectrum is markedly reduced. The ICCD detector is precisely synchronized with the laser pulse. the high power of the pulsed lasers can greatly enhance the signal-to-noise ratio. www. The short wavelength laser can enhance the Raman scattering intensity. various high temperature Raman spectroscopic techniques have been developed.com In-Situ Investigation of the Melt Structures … 29 temperature Raman spectroscopy suffers from the intense black-body radiation from samples and furnaces that often covers the useful Raman signals. an Intensified Charge Coupled Device (ICCD) detector was applied in a high-temperature Raman spectrometry by You et al. and then the stray light outside the pulse duration is eliminated.ebook777. (2) accumulated time resolution technique [27]. Figure 2. By using pulsed laser sources. A typical experimental system for the study of high-temperature melt structures. including: (1) spatial resolution technique [26].

Furthermore. (4) The powerful tool is still scarce for the theoretical analysis on borate Raman spectra. The growth cell is fabricated from high-grade stainless steel and consists of a water jacket surrounding the main sample chamber. and the spatial resolution is less than 2 µm. If the calculated method is reliable. The excitation source is the 532 nm line of a Q-switch pulsed SHG-Nd: YAG laser. The heating system provides a horizontal temperature gradient in the boat. (3) the weakness of high-temperature Raman peaks. Raman spectra are recorded on the high-temperature Raman spectrometer (Jobin Y‘von LABRAM HR800 in our experiments) with a back scattering configuration. and has been used to investigate the borate melt structures that are difficult to obtain by conventional experimental methods alone. Raman peaks of a borate melt are structurally assigned by comparison with the spectra of borate crystalline compounds based on the assumption that the structural units present in melts resemble those present in the crystalline compounds [23. 3. and the Raman scattering light is collected by a confocal lens system. Traditionally. The triangular and/or tetrahedral boron–oxygen moieties often polymerize to various poly-anions by sharing oxygen atoms. 31].com 30 Songming Wan A typical experimental system for the study of borate melt structures comprises two components (see Figure 2) [30]: a Raman spectrometer and a crystal growth cell. However. THE DENSITY FUNCTIONAL THEORY METHOD Although high-temperature Raman spectroscopy is the best experimental technique to study borate melt structures.free ebooks ==> www. a Raman peak sharp at low- temperatures often broadens at high-temperatures. The main difficulties arise from: (1) the great structural diversity of borate melts. The laser beam is introduced into a sample. A platinum boat with the size of 5 × 10 × 20 mm3 is placed in the center of the chamber and heated on the right side by a platinum wire winding.ebook777. ab initio calculation is regarded as the alternative to the traditional approach. and overlaps with adjacent peaks. different poly-anions probably give rise to Raman peaks in the same region. such an approach will be invalid if a melt structure is different from any crystalline compound structure. (2) the complexity of borate Raman spectra. the conversion of the vibrational peaks seen in a Raman spectrum into the structural information remains difficult. and the calculated Raman spectrum of a guessed melt structural . The measuring temperature of the experimental system is up to 1200 oC. Even worse.

and Sham nearly 50 years ago [34]. made by Baroni. and Raman peak intensity of borate glasses [32]. However. and the exchange and correlation effects are included within either the local density (LDA) or the generalized gradient (GGA) approximation. usually performed using the Gaussian program. Raman frequencies are computed by diagonalization of dynamical matrices. A larger amount of valuable information about borate melt structures has been obtained. In the framework of DFPT. The Cambridge Sequential Total Energy Package (CASTEP) [38]. (2) The solvent effect (the interactions of the clusters with the surrounding). the pseudo-potentials are used to describe the electron–ion interactions. Raman spectra can be accurately calculated by coupling a standard DFT method with a linear response phonon model. The package uses a total energy plane-wave pseudo-potential method. is hard to be formulated in the Hartree–Fock method. In the mathematical model used in the method. Breakthrough studies on borate melt structures and Raman spectra benefit from the development of the density functional theory (DFT) which was established by Hohenberg. the method has several drawbacks leading to relatively poor prediction of melt structures. which severely influences the calculated results. From the beginning of this century. is regarded as the most validated commercial software to predict material structures and their Raman spectra. originally developed in the Theory Condensed Matter Group at Cambridge University. Raman frequencies. the electronic wavefunctions are expanded through a plane-wave basis set. is the old method widely used to calculate the equilibrium structures. one can conclude that the guessed model can be used to describe the melt structure. The Hartree–Fock method. CASTEP currently provides two different methods (the DFPT method and the ―finite displacement‖ method) for calculating Raman frequencies.free ebooks ==> www.com . The density functional perturbation theory (DFPT).com In-Situ Investigation of the Melt Structures … 31 model is consistent with the experimental Raman spectrum. In www. In CASTEP. [33]. extends the scope of the DFT Hamiltonian [35–37]. Gonze and their co-workers. for example: (1) The method is suitable for isolated small clusters. (3) The method often results in systematic errors of calculated Raman frequencies due to the lack of good modeling of the electronic orbitals. but not for the larger borate clusters that are very likely to exist in borate melts. the method has been extended to study borate melt structures by You et al. Kohn.ebook777.ebook777. and the Raman activity tensor/intensity of each mode is given by the derivative of the dielectric permittivity tensor with respect to the mode amplitude. and uses a hybrid method combining DFPT with the ―finite displacement‖ method for calculating Raman activity tensors/intensities.

polarizers. therefore. The DFT method has been applied recently to a larger number of crystalline materials. β-BBO crystals are commonly grown from the Na2O/NaF flux due to the phase transition [12]. and beam splitters. Good agreement with experimental results was achieved [39]. along with the BMBO crystal. MELT STRUCTURES IN SOME BORATE CRYSTAL GROWTH SYSTEMS (1) Melt Structures in the Ba2Mg(B3O6)2 and BaB2O4 Crystal Growth Systems The Ba2Mg(B3O6)2 (BMBO) and high-temperature phase BaB2O4 (α-BBO) crystals are excellent uniaxial crystals with large birefringences. we attempted to apply CASTEP to simulate the Raman spectra of borate melts. can be grown by the Czochralski or Kyropoulos method [40]. Unlike the two crystals. demonstrated that the α-BBO crystals doped with a small amount Sr2+ are stable at room temperature. the CASTEP calculation can provide the atomic displacements of each peak/mode in a Raman spectrum. Very little research has been carried out on the melt structures in the three crystal growth systems although the structures are believed to be essential to understand various growth phenomena. I am sure that the CASTEP method combining with high- temperature spectroscopy will open a new way to explore the structures of borate and other inorganic melts. the Sr2+-doped α-BBO crystal. The three crystals are all made up of alkaline earth ions and [B3O6]3– planar six-membered rings. and found that the results obtained by CASTEP are much better than those obtained by other traditional methods. a wide transparence range and good physicochemical stability. The following are the last applications of high-temperature spectroscopy and the DFT method in the borate melt structure studies. Wang et al. Considering that CASTEP has been used to study liquids and melts are special liquids existing under high-temperature conditions. 4.com 32 Songming Wan addition. beam displacements. especially those used in the deep ultraviolet region [4–6]. but the BaB2O4 crystal undergoes a phase transition at about 925oC. The low-temperature phase BaB2O4 (β-BBO) is an excellent NLO crystal widely used in laser and optoelectronic devices [3].free ebooks ==> www. For the β- .ebook777. Both of them can be employed to produce various prisms. The BMBO and BaB2O4 crystals melt congruently.

The site group analysis results Figure 3.com In-Situ Investigation of the Melt Structures … 33 BBO crystal growth system. but molecular dynamic (MD) studies showed that the [B3O6]3– rings in the crystal structure quickly disappeared in the melt just after the crystal melted and formed long chain structures [42]. The focus of their disputes is whether the [B3O6]3– rings exist near the growth interface. Site group analysis for the BMBO lattice modes www. First of all. and further presumed that planar [B3O6]3– rings were the growth units [41]. and gave more accurate assignments for its vibrational modes [43]. the mode assignments of the [B3O6]3– ring are still in debate.com . we re-investigated the characteristic Raman peaks of the [B3O6]3– ring. Table 1.ebook777. Using the BMBO crystal as an example. we need to identify the characteristic Raman peaks of the [B3O6]3– ring. proposed that a melt with a pre- ordering structure formed near the growth interface during the crystal growth process. Although the Raman spectrum of the β-BBO crystal has been investigated extensively.free ebooks ==> www.ebook777. Kouta et al. Atomic displacements of three symmetrical vibrations of [B3O6]3– six- membered rings.

Figure 4. The Raman peaks arising from the internal modes of the [B3O6]3– ring are above 220 cm–1. 10Ag + 10Eg are Raman active. Measurement positions (top) and their corresponding Raman spectra (bottom). The inset is the structure of the [B3O6]3– ring. among them. . and the external below 220 cm–1.ebook777. and 1510−1570 cm–1 the breathing mode of the boron atoms.com 34 Songming Wan (Table 1) show that the total lattice modes of the BMBO crystal are 10Ag + 11Au + 10Eg + 11Eu. positions b is in the crystal and 10 μm from the interface. The peak at 636 cm–1 is assigned to the breathing mode of the boron and extra-ring oxygen atoms. All of them belong to the Ag mode.free ebooks ==> www. All of the Raman active modes have been identified on the basis of the CASTEP calculated results. Position a is in the melt and 10 μm from the interface. as shown in Figure 3. Two strong Raman peaks located at 636 cm–1 and 768 cm–1 (calculated values) and four Raman peaks in the range of 1510−1570 cm–1 are the characteristic Raman peaks of the [B3O6]3– ring. 736 cm–1 the breathing mode of the intra-ring oxygen atoms.

As mentioned above. the laser beam was focused on different positions near the crystal−melt interface to study the structures of the crystal and the melt.free ebooks ==> www. we thus conclude that the [B3O6]3– rings are the dominant boron–oxygen structural units in the melt near the BMBO crystal–melt interface [44]. Two wide bands in the range of 600–850 cm–1 and 1300–1600 cm–1 appear in the BMBO melt Raman spectrum. The bottom right illustration is the structure of the [B3O6]3– ring. Both of them can be attributed to the merger of the characteristic Raman peaks of the [B3O6]3– rings. One such slice was then mounted in the boat with its right part heated to the temperature just above its melting point (1095 oC). and then a stable crystal−melt interface was produced.ebook777. and 5 μm. A typical α-BBO crystal–melt interface with the measurement positions (upper right) and their corresponding Raman spectra (left). the temperature was slowly decreased to allow the crystal to grow gradually to the right. Finally. The intensity of the Figure 5. respectively. 55 μm and 155 μm from the interface. the bands arise from the merger of two Ag modes whose Raman peaks are centered at around 640 and 770 cm–1. www. Similarly. the [B3O6]3– rings were found as the main structural units in the melt near the α-BBO crystal–melt interface [45].com . C and D are in the melt.ebook777. The melt structures near the α-BBO crystal–melt interface were studied in the same manner. After that. positions B. Position A is in the crystal and 25 μm from the interface. It is noteworthy that the 600–850 cm–1 bands of the two melts peak at the different positions.com In-Situ Investigation of the Melt Structures … 35 A BMBO single crystal grown by the Kyropoulos method was cut into slices slightly smaller than the platinum boat (see Figure 2). as shown in Figure 4.

ebook777. 640 cm–1 peak is much stronger than that of the 770 cm–1 peak in the α-BBO melt Raman spectrum (see Figure 5). The . the growth rate of a crystal face is proportional to its attachment energy (Eatt. and thus present in the final morphology (see Figure 6). On the basis of the experimental results. the crystal structure breaks into Ba2+ ions. indicating both of the Ba–O and Mg–O bonds are the weak bonds in the crystal structure. The face that grows slower appears to be the larger developed face. the BMBO crystal morphology (growth habit) was explained by the attachment energy theory [44]. which results in the merged band peaking at lower frequency in the α-BBO melt Raman spectrum as compared with that in the BMBO melt Raman spectrum. defined as the energy released when one additional growth slice of thickness dhkl is attached to the crystal face identified by the Miller indices hkl). During the melting process of the BMBO crystal. In principle. and (c) the b axis. Mg2+ ions and [B3O6]3– rings.free ebooks ==> www. the morphology of a crystal is determined by the relative growth rates of different crystal faces. (b) the a axis. The (001) (101) and (012) crystal faces that are linked by the weak bonds have smaller attachment energies and slower growth rates. Packing arrangement of BMBO crystal structure as viewed along (a) the b axis. Based on the Hartman–Perdok theory. and BMBO crystal morphology (bottom right).com 36 Songming Wan Figure 6. but comparable in the BMBO melt Raman spectrum.

The platinum boat was heated slowly until the raw material melted completely and the crystal began to melt. as a flux. An isomerization reaction taking place near the β-BBO crystal–solution interface.ebook777. and {10 ̅ 10} faces. a stable crystal–solution interface was established. the high- temperature Raman spectra were recorded from different positions near the crystal–solution interface [46]. {01 ̅ 4}. The CASTEP calculations further proved that the wide band in the range of 950−1250 cm–1 is associated with a special chain-type [B3O6]3– group. i. The predicted results both of the BMBO and α-BBO crystals are in good agreement with the observed. The [B3O6]3– rings play a role of the basic units of the β-BBO crystal growth. a new β-BBO crystal grew gradually from the old crystal surface. After that. {10 ̅ 2}.com In-Situ Investigation of the Melt Structures … 37 Figure 7. According to the results. Na2O. a small slice of the β-BBO single crystal was placed on the cool side of the platinum boat. www. The experimental results show that a wide band in the range of 950−1250 –1 cm presents in the Raman spectrum of the bulk solution. which present in the final crystal morphology.ebook777. the raw material (70 mol% BaB2O4−30 mol% Na2O) was placed on the hot side. finally. the β-BBO crystal growth habit (morphology) can be explained very well.com .free ebooks ==> www. the [B3O6]3– rings and Ba2+ cations stack mainly along four types of PBCs. The thickness of the boundary layer is less than 85 μm. By slowly decreasing the temperature.e. The spectral difference clearly indicates a boundary layer existing near the β-BBO crystal–solution interface. The chain-type [B3O6]3– groups transforms to the ring-type [B3O6]3– groups in the boundary layer (see Figure 7). The four PBCs constitute three F faces. At the α-BBO crystal–melt interface. is widely used to produce large-sized and high-quality β- BBO crystals [12]. α-BBO crystal morphology was explained by the periodic bond chain (PBC) theory [45]. In order to simulate the β-BBO crystal growth. but disappears in the Raman spectra of the solution near the interface.

. Figure 8. Both of the crystals are built up of [B3O3Ø4]– six-membered rings (see the bottom right illustration in Figure 8. Compared with the LBO crystal. Ø = bridging oxygen atom) and alkali metal ions. The bottom right illustration is the isomerization reaction taking place near the CBO crystal–melt interface. CBO melts congruently but LBO melts incongruently. but LBO crystals must be grown by the flux method [12].free ebooks ==> www. The LBO crystal allows temperature-controllable non-critical phase matching (NCPM) in a wide wavelength range. Thus.ebook777. and is a material of choice for high power lasers [47]. Position A and B are in the melt. and their corresponding Raman spectra (left).0 kg have been produced [51–53]. Significant progress in the growth of larger LBO crystals has been achieved since 1996 with the development of MoO3-based fluxes [50]. The B2O3 flux was firstly reported in 1989 by Chen et al. [49]. and was widely used to industrially produce LBO crystals in the following decade. Using the fluxes. respectively.com 38 Songming Wan (2) Melt Structures in the CsB3O5 and LiB3O5 Crystal Growth Systems Both CsB3O5 (CBO) and LiB3O5 (LBO) are excellent NLO crystals due to their relatively large effective NLO coefficients. a high laser damage threshold. A typical CBO crystal–melt interface with the measurement positions (upper right). the CBO crystal is more efficient for the generation of the third harmonic of the 1064 nm radiation of Nd: YAG lasers [48]. and 5 μm and 100 μm from the interface. and a wide optical transparency range. CBO crystals can be grown by the Kyropoulos method. high-quality LBO crystals with the weight up to 2.

the CBO crystal Raman spectrum was studied by CASTEP [54]. was carried out for establishing a stable CBO crystal–melt interface. 20 and 5 µm. Figure 8 shows the Raman spectra recorded from different positions near the CBO crystal–melt interface [30].com In-Situ Investigation of the Melt Structures … 39 Figure 9. the spectral changes imply that an isomerization reaction between [B3O3Ø4]– rings and [B3O4Ø2]– rings takes place near the crystal–melt interface. A typical LBO crystal–solution interface with the measurement positions (top) and their corresponding Raman spectra (bottom).ebook777. www. as shown in Figure 8.free ebooks ==> www. In order to understand the structural origins of CBO crystal Raman peaks. 50.com . b. c and d are 100. and related to the breathing vibration of the [B3O3Ø4]– rings (760 cm–1) and the bending vibration of the BØ4 units in the [B3O3Ø4]– rings (380 cm–1). as described in the above α-BBO experiment. respectively. According to the CASTEP results of the CBO crystal. The distances from the interface to the measurement position a. the crystal 380 cm–1 peak vanishes. but the 760 cm–1 band remains. The CASTEP calculated results show the crystal characteristic peaks are located at around 760 cm–1 and 380 cm–1. When the measurement position moves from the crystal to the melt. A similar experimental process.ebook777.

and packing arrangement of CBO crystal as viewed along the a axis (right). The bridging oxygen atoms between two [B3O3Ø4]– rings are pointed by the arrows. Considering the influence of the surrounding. we established a crystal–solution coexisting system constituted by the LBO crystal and the Li2O·4B2O3 high-temperature solution. the continuous three-dimensional crystal network collapses and transforms into spiral chains. the isomerization reaction between the [B3O3Ø4]– and [B3O4Ø2]– rings was also found in the LBO crystal boundary layer. The calculated frequencies and intensities were corrected with a scaling factor (0. the two bridging oxygen atoms in the [B3O4Ø2]– ring are saturated by two hydrogen atoms. Figure 10. the CBO melt Raman spectrum was simulated by using the Gaussian software [54].free ebooks ==> www.ebook777. which reveals a boundary layer with the thickness of about 50 μm existing near the interface. Similarly to the structural changes observed near the CBO crystal–melt interface. The simulation was based on a traditional restricted Hartree–Fock method with the 6–31G(d) basis set. .8970) and Bose–Einstein population factors. the CBO melt structure near its melting point was deduced by You et al. [54]. Morphology of CBO crystal grown from the CBO melt (left). The calculated results provided the valuable vibrational information of the [B3O4Ø2]– ring. The results are shown in Figure 9. respectively. When the crystal melts. On the basis of the [B3O4Ø2]– chain model. The solution structures near the crystal–solution interface were investigated by high-temperature Raman spectroscopy [55]. On the basis of the isomerization reaction. In order to simulate the LBO crystal growth from the B2O3 flux. its basic unit is a [B3O4Ø2]– ring. and further interpreted the Raman spectral changes taking place in the crystal melting process.com 40 Songming Wan The isomerization reaction was also found during a CBO crystal melting process.

55].com . the CBO or LBO crystal growth is accompanied by the conversion from the [B3O4Ø2]– rings to the [B3O3Ø4]– rings.free ebooks ==> www. As compared with the crystal Raman band. the faces only containing the B4–Ø weak bonds are parallel to the (101). The BIBO melt Raman bands are located around 370 cm−1. Meanwhile. (0 ̅ ). the strong crystal peak located at 574 cm−1 disappears when the crystal melts. a high damage threshold and a large angular acceptance [56].ebook777. and should thus be a larger developed face.). ( ̅ ). Its crystal structure is made up of Bi3+ layers and boron–oxygen layers. but not with the {001} faces. The crystal Raman peaks in the high frequency region (1200–1500 cm−1) are associated with the stretching vibrations of the boron–oxygen bonds in the boron–oxygen triangles. some important crystal Raman peaks were assigned on the basis of the CASTEP calculated results. and (01 ̅ ) faces (The case of the (011) face is shown in Figure 10. The crystal melts congruently at 708 oC. BIBO crystallizes in the monoclinic space group C2. In order to interpret the structural origins of the spectral changes. the melt Raman band in the range of 1200–1500 cm−1 increases in intensity. the face only containing BØ4 tetrahedra has a lower attachment energy and a lower growth rate. which reveals that the B4–Ø bonds (B–Ø bonds of BØ4 tetrahedra) are weak bonds in the crystal structures.ebook777. a wide transparency range. (10 ̅ ). The 574 cm – 1 (calculated) www. According to the CBO crystal structure. A similar analysis reveals that the LBO crystal tends to grow with the well-developed {011} and {201} faces. possessing exceptionally large NLO coefficients. Therefore. The experimental process is similar to that in the study of the BMBO melt structure. and should thus be the larger developed faces. the boron–oxygen layer is constituted by boron–oxygen triangles and tetrahedra in a ratio of 2:1 [57]. 630 cm−1. High-temperature Raman spectroscopy and CASTEP have been used to study the melt structure in a BIBO crystal–melt coexisting system [58]. These predicted growth habits are all in good agreement with the experimental results. (3) The Melt Structure in the BiB3O6 Crystal Growth System The α-BiB3O6 (BIBO) crystal is an outstanding NLO material. On the molecular level. and thus can be grown by the Kyropoulos method [12]. and in the range of 1200–1500 cm−1.com In-Situ Investigation of the Melt Structures … 41 The structural evolution taking place near the crystal–melt interfaces can be used to explain the growth habits of the CBO and LBO crystals [30. (011).

as shown in Fig 11. The spectral changes reflect that the Bi–Ø bonds disappear due to the crystal melting.ebook777. and the concentration of the boron–oxygen triangles in the BIBO melt is more than that in the BIBO crystal. Experimental and calculated Raman spectra of BIBO crystal (bottom left). The CASTEP calculations were carried out to simulate the BIBO melt Raman spectrum based on the structural unit [58]. 934 cm−1.free ebooks ==> www. 1222 cm−1. value: 561 cm−1) crystal peak arises from the Bi–Ø symmetric stretching vibration of the BiØ4 pyramids. The melt is made up of Bi3+ ions and special [B3O5Ø2]3− (Ø = bridging oxygen) structural units (see Figure 12 and 13) which further polymerize into [B3O5Ø2]n chains by sharing oxygen atoms. and 1461 cm−1. and the atomic displacements of the calculated peaks located at 561 cm−1. The new boron–oxygen triangles come from the transformation from the four-fold coordinated boron atoms (in the crystal) to the three-fold coordinated boron atoms (in the melt). On the basis of the BIBO crystal growth habit.com 42 Songming Wan Figure 11. a polymer model was proposed to describe the BIBO melt structure [58]. The calculated melt Raman spectrum shows good agreement with the experimental (see .

All of the vibrational bands in the melt Raman spectrum are assigned (see Figure 13). www.ebook777.com . Atomic displacements of four main peaks in the calculated BIBO melt Raman spectrum. (c) calculated Raman spectrum broadened by Gaussian line shape function with a FWHM of 5 cm−1.free ebooks ==> www.com In-Situ Investigation of the Melt Structures … 43 Figure 12). Inset: BIBO melt structure. (a) Experimental Raman spectrum. (b) calculated Raman spectrum broadened by Gaussian line shape function with a FWHM (full width at half maximum) of 50 cm−1.ebook777. Figure 12. Experimental and calculated Raman spectra of BIBO melt. Figure 13.

the Raman peaks in the 600–850 cm−1 range are assigned to the breathing vibrations of the boron–oxygen six-membered rings. (1) the intense crystal peaks located around 720 cm−1 and in the range of 900–1200 cm−1 disappeared. the bands in the range of 1200–1500 cm−1 arise from the stretching vibrations of the boron– oxygen (B–Ø or B–Ø) bonds in the boron–oxygen triangles. and Z = 8. the band located around 630 cm−1 is assigned to the bending vibrations of the [B3O5Ø2]n chain. this is the first study to determine a high-temperature melt structure by the means of Raman spectroscopy combined with the DFT method.com 44 Songming Wan The strongest band below 400 cm−1 is mainly attributed to the wagging vibration of the side BO2Ø triangle as a whole. the LTB crystal Raman spectrum was studied by CASTEP [61]. as shown in Figure 15. and also used for the generation of the fourth and fifth harmonics of Nd: YAG lasers [59] and for neutron detection [11].477 Å. The crystal belongs to the tetragonal space group I41cd with the unit cell parameters a = 9. (2) the high-frequency peaks in the range of 1300–1500 cm−1 anomalously blue-shifted (see Figure 14). (4) The Melt Structure in the Li2B4O7 Crystal Growth System The Li2B4O7 (LTB) single crystal is a superior substrate for surface and bulk acoustic wave devices [10].286 Å. The spectral changes during the melting process indicate that: (1) boron– oxygen six-membered rings remain in the melt although their structures might be different from those in the LTB crystal.ebook777. (2) new structural units with extra- ring B3–O bonds (not B3–Ø bonds) present in the LTB melt because strong . After the LTB crystal melting. According to the CASTEP results. High temperature Raman spectroscopy was used to investigate the melt structure in a LTB crystal–melt coexisting system [61]. The experimental process is similar to that in the study of the BMBO melt structure. c = 10. To the best of our knowledge.free ebooks ==> www. the high-frequency peaks located around 1436 cm−1 are assigned to the stretching vibrations of the extra-ring B3–Ø bonds (B–Ø bonds of boron−oxygen triangles). the intense peaks located in the range of 900–1200 cm−1 mainly arise from the asymmetrical vibrations of the BØ4 units. In order to understand the structural origins of the spectral changes. The LTB crystal melts congruently and is often grown from a LTB melt by the Czochralski or Bridgman method [12]. Its structure is made up of [B4O5Ø4]2– tetraborate groups and Li+ ions [60].

free ebooks ==> www.ebook777. Raman spectra of LTB crystal and melt. DFT calculations verified the melt structural model and provided accurate assignments for the vibrational bands present in the LTB www. Figure 14.com In-Situ Investigation of the Melt Structures … 45 Raman peaks located around 1500 cm−1 are often attributed to the stretching vibrations of the extra-ring B3–O bonds.com . its basic unit is the [B4O6Ø2]2− group which is formed by a [B3O4Ø2]− six-membered ring and a [BOØ2]− triangle linked by a bridging oxygen atom. (a) Crystal Raman spectrum recorded at 30 oC. Atomic displacements of three important crystal Raman peaks.ebook777. (c) melt Raman spectrum recorded near the melting point. A structural model has been proposed to describe the LTB melt on the basis of the above structural analysis [61]. (b) crystal Raman spectrum recorded at 500 oC. Figure 15. The melt is made up of polymer- like boron–oxygen chains.

Atomic displacements of five strong peaks in calculated LTB melt Raman spectrum. (a) Experimental Raman spectrum. Experimental and calculated Raman spectra of the LTB melt. (b) calculated Raman spectrum broadened by Gaussian line shape function with a FWHM of 200 cm−1. (c) calculated Raman spectrum broadened by Gaussian line shape function with a FWHM of 10 cm−1. . the Raman band in the range of 600–800 cm−1 is mainly related to the out-plane bending vibrations of the boron–oxygen triangle and the breathing vibration of the six- membered ring. The Raman band in the range of 250–500 cm−1 is attributed to the motions of the Li+ ions. the Raman band in the range of 1300–1600 cm−1 primarily arises from the stretching vibrations of the extra-ring B3–O bond. Figure 16.free ebooks ==> www.ebook777.com 46 Songming Wan melt Raman spectrum (see Figure 16 and 17) [61]. Figure 17.

free ebooks ==> www. is the most important micro-process taking place near the CBO. the continuous three-dimensional crystal networks collapse and transform into special borate−oxygen chains that have not been found in borate crystal structures. can exist in not only crystal structures but also the corresponding melt structures. ACKNOWLEDGMENTS The author thank the National Natural Science Foundation of China (Grant No. arising from the transformation between four-fold and three-fold coordinated boron atoms. such as [B3O6]3– rings. High-temperature Raman spectroscopy combining with the DFT calculation have successfully been applied to study the melt structures in some borate crystal growth systems. www.ebook777. (3) When the CBO. the DFT calculation is a reliable theoretical method to establish the links between Raman spectra and micro-structures of crystals and melts.com In-Situ Investigation of the Melt Structures … 47 CONCLUSION High-temperature Raman spectroscopy is an effective experimental tool to in-situ investigate high-temperature melt (solution) structures. BIBO. (4) Boundary layers whose solution structures are different from that in the bulk solutions have been found around the LBO and β-BBO crystal−solution interfaces. The following are some important conclusions drawn from our research: (1) Stable boron−oxygen groups. (2) An isomerization reaction. The conclusions drawn in the chapter can help us deeply understand the macro-properties of borate melts and the micro-processes of borate crystal growth.ebook777. and LTB crystal−liquid (melt or solution) interfaces. 50932005 and 51372246) for the financial support. LBO.com . BIBO. the predicted results are all in good agreement with the experimental. (5) The melt structures near the crystal–melt interfaces can be used to predict borate crystal growth habits. and LTB crystals melt. The boundary layers are about 50 μm in thickness. I believe that the experimental and theoretical methods provided here can be extended to study the melt structures of many other inorganic compounds more than borates.

C. G. Zhou J. New York. Abernathy. [2] ICSD—Inorganic Crystal Structure Database. Q. [14] G. and Y. L. D. T. [5] S. Y. E. J. [8] Z.. van Eijk. [7] N. in Proceedings of the International Conference on Inorganic Scintillators and their Applications: Shanghai. S. Heller. Zhong. 1998. 1986). M. H. and J. Van der Veen. 59. Wu. Mater. Peters. Whatmore. Zhou. Electron. Gan. D. [6] R. A. D. Frechette. A. M. Deng. 17. F. Lin.. pp. 10. Rev. [9] Y. Fei. and F. Element. 191. Cryst.ebook777. M. Growth Charact. Zabudko. D. and N. Prog. 39−98. C. p. [13] E. A. Henderson. Ginkin. p. 3. Kartavykh. 1998. Cryst. 1228−1231. [3] P. 270. Lin. 252. 1−38. Xu. 1981. 1997. Becker. Wan. Y. J. Mater. 2006. 1277−1279. Huang. Chai. J. Y. and Y. Tan. Wang. and M. Chen.. Zwanenburg. Young. 379−381. Boschke (Springer-Verlag.free ebooks ==> www. Luo. Vries. G. Shorrock. 329−339. J. J. 2005). M. 5421−5424. E. Growth. 31. edited by L. Z. Song. F. 517−519. Lett. Y. 2012. F. 131. Leonyuk. Huisman. Opt. I. Kreidl (Plenum Press: New York.‖ in Materials Science Research. [17] V. National Institute of Standards and Technology and Fachinformationszentrum Karlsruhe. 86. P. W. Y. K. D. 021115. B. Calas. Cryst. Q. Virgina. Riebling. J. Lett. 1997. T. 390. Derry. N. edited by F.‖ in Topics in Current Chemistry. V. S. Pye. 517−519. Zhang. I. 12. W. Growth. Chen. Ebbers. Q. [10] R. and B. pp. X. 979−992. Q. F. Ni. and T. Nature. T. Cryst. China. Ma. 269−273. T. 14. D. Leonyuk. V. Karas (Nova Science Publishers.. O‘hara. Q. 31. X. Ainger. Vol. Li. and I. X. 2006. [11] C. ―Structural Chemistry of Boron and Silicon. 1995. and J.com 48 Songming Wan REFERENCES [1] G. 22–25 September. and L. Phys. I. Y. 2. 1987. Lett. W. Adv. X. S. F. F.‖ in New Developments in Crystal Growth Research. ―Borate Glass. [12] S. Stebbins. 2004.. 179−278. [16] W. . Hu. Vol. 1978). Liao. 2005. Lett. M. 387. Jovanovic. 2008. ―The Growth of Borate Crystals. [15] W. A. Phys. K. edited by G. Growth 2003. Z. Xu. [4] G. D. Curtin. J. CrystEngComm. 11−12. Appl. J.

You. L. H. Phys. 1998. Chen. and A. R. [30] S. Jenkins. 501−502. Wan. A. ―Laser Raman spectroscopy. T. 4718−4732. 1−8. L. 8. 1995). Jiang. Spectrosc. 137−168. L.. Phys. Q. [33] J.‖ in Growth of Crystal. [34] P. Fu. Kudryavtsev. 2010. L. P. [22] S. Landron.. Voron‘ko. [19] C. Vol. M. Osipov. 321. [25] M. Solid Earth. 52. C. Kunimine. H. Funamori. Zhang. Kauffmann... www. K. edited by J. 96. 1928. Yamamoto. Breuer. N. B. 199−217. Tobin. 1971). J. 36. Nature. Kaplan.S. E. L. W. Krishnan. [32] T. [27] Yu. Greaves. in Synopsis of International Conference on Raman Spectroscopy: Gold Coast.ebook777. O. and W. 321−332. Yoshimura. H. X. A.‖ in Chemical Analysis. S. 310. L. and S. L. Uchino. and D. Hennet. J. pp. Zhang. C. 10848– 10851. 1224−1228. S. Australia. Kakihana. J. Yoko. 1992. and M. Y.com . 105. Rev. Shimidzu. Dingwell (Mineralogical Society of America: Washington DC. Yamane. C. You..com In-Situ Investigation of the Melt Structures … 49 [18] N. Y. Osipova. 1991). [21] J. Wu. ―Study of Melt Structure and Crystallization Processes by High- temperature Raman Spectroscopy. Gonze. and K. Stebbins. D. Hohenberg. S. 4839−4842. H. Appl. and J. edited by S. Raman. Y. Kikegawa. and M. D. K. 41.V. 51. 224−225. McMillan. Wu. J. pp. Osiko. M. 2004. Jiang. Non-Cryst. J. Zhao. Zhang. Lett. Sobol‘. a Series of Monographs on Analytical Chemistry and Its Application. and H. Q. 2005. 32. J. Rühle. Fujimori. Phys.ebook777. Growth Des. Rev. [23] T. Scheu. Science 2005. [31] A. Vol. 2008. [35] X. Hou.. pp. 1997. Y.‖ in Review in Mineralogy. 864−871. pp. Cryst.. Chem. T. Bagdasavov. Kolthoff (Wiley-Interscience: New York. B. G. J. Yin. Stebbins. Rev. and M.free ebooks ==> www. Chen. and T. Mysen. [24] C. K. O. 136. and L. Z. Xu. and T. 412−414. Phys. and K. P. Oh. 405. F. You. D. 191−246. and E. Geophys. A. M. Solid State Ionics. Q. P. Y. Res. C. Elving and I. D. 2004. L. A 1995. G. Raman Spectrosc. N. Bonzel. Kohn. 86. and A. V. F. G. ―Dynamics and Structure of Silicate and Oxide Melts: Nuclear Magnetic Resonance Studies. [26] B. Yashima. 91−96. Soper. Geol. Knauff. B 1964. Xu. 8–13 August. [20] U. V. B 1990.16. M. 1−30. Lube (Consultants Bureau: New York. [29] M. Physica B. F. H. 121. 2013. Lu. Yano. Solids. Frantz. Coutures. P. edited by P. Wu and S. 237−249. Shibata. C. 661−663. T. 109. [28] J. 1096−1114. 2001. Yagi. Rev.

J. Fu. M. Zhang. Appl. E. Y.free ebooks ==> www. 1989. A. Porezag. Parfeniuk. L. 1991. Q. C. and K. Wan. 58. 158. A. Sinica. Zhang. Yin. 945−949. and S. X. [39] V. T. J. 2011.. S. 220−225. C. Pickard. Fjeldsted. Wan. Sun. J. J. J. Milman. [45] S. Huang. Liang. Q. [52] A. Z. R. Y. Yin. L. Gu. Appl. 363. Imoto. 54. M. 22−35. Rev. J. You. J. L. [43] X. C. J. S. 40. [41] H. F. and M. Probert. Kong. Villeval. Perlov. J. Cheng. L. Cryst. Y. Sun. 133-137.: Condens. Xu. C. Y. S. J. Kondilenko. Zhang. and Y. Durst. F. Opt. Yates. F. [37] D. M. 1579−1581. C. Li. 2007. Lv. 1996. 514−533. [47] J. and S. [48] Y. 2001. Hasnip. Pan. [50] C. Phys. 47. T. (THEOCHEM) 2010. 2717−2744. Growth. J. J. G. Z. Growth. Kononova. Growth. L. Z. Weinberg. Q. J. Kouta. Perlov. and B. K. G. 2013. . C. Y. de Gironcoil. Chen. R. Wan. Y. Mol. 739−744. G. C. J. V. L. M. Chen. Zhang. D. 1−3. Wang. Growth. Loiacono. Y. Matter. and J. D. You. Chen. C. C. Sanchez. 1997. Segall. J. Phys. Segall. 2002. (Chinese) 1984. S. Waseda. 312. S. Clark. Lupinski. B. and M. Cryst. Shen.ebook777. Growth. 128. and D. J. 331. Zhao. X. S. 1774−1778. Czechowicz. S. Lett. 954. 107−111. Zhang. K. 335. Chen. D. H. [53] Z. Wu. S. P. L.. K.. R.. C. Hasnip. Pickard. Cryst. J. Jiang. L. [51] I. Struc. S. G. and B. Appl. Wang. Kokh. J. Tang. Wu. [46] S. 73. [38] M. I. Y. Lv. 503−508. J. S. N. J. 1840−1842. V. Cryst. Zhang. T. Samarasekera. Wan. 725−729. Lent. 371. P. L. J. X. Huang. Cryst. Wang. Growth. D. Ph. S. J. Hao. I. 2010. Han. S. J. 128. 515−562. 1993. Clark. Refson. Hu. Lindan. 2010. 616−621. Y. Probert. S. X. and Y. Kuwano. [49] C. 7830−7836. Growth. Cryst. Wu. and X. S. Pederson. M. Acta Chim. Growth. X. P. Gao. X. J. Lin. Soc. Edel. J. M. S. and Y.com 50 Songming Wan [36] S. J. and Q. 938−944. and M. You. Livneh. and P. J. V.. Cryst. R. Jiang. Phys. 2013. 2014. T. Baroni. D. M. Payne. Liu. Phys. C. [40] G. Giannozzi. P. Opt. Corso. Lett. Nikolov. M. P. D. Am. [42] H. Kokh. L. K. Z. and C. Cryst. Ogawa. 14. D. A. Wu.. Lin. Rev. Mennerat. Mod. G. 22. J. 6. [44] X.. and S. Vlezko. 1993. Yu. G. T. P. J. 42. Y. Zhang. Yue. B 1996. Cryst. Cryst. S. J. Y. J. S.

L. [60] S.free ebooks ==> www. and S. Zhang. Fu. [59] R. B. J. X. Sect. Yamanouchi. Liebertz. T. Fukuda. T. Phys. G. 2014. 1984.. G. Y. Wang. [56] H. Zhang. Wan. and J. L. Z. 16. S. S. Komatsu. CrystEngComm. K. L. You.ebook777. Bohaty. Z. and P. [55] D. F. Zhang. M. Wan.com . X. S. Y. M. Natalis.. Bohaty. Y. and P. Acta Crystallogr. Zhang. Wan. Tang. L. J. Sun. Wu. Ji. Sarukura. You. CrystEngComm. J. Hellwig. 109. 290−296. S. 70. and S. Fu CrystEngComm. Liu. M. You. C. 249−251. Commun. and K. Hou... 2011. Yin. 13. L. L. Tang. Sassa. Segawa. N. 40. Z.. 1997. Alloys Compd. 15. C. L.ebook777. Lett. Q. You.com In-Situ Investigation of the Melt Structures … 51 [54] M. S. Jurii. Y. 343−344. M. 5239−5242. Sun. Liebertz. and L. 2011. Sugawara. L. Wang. Yin. L. Izumida. S. J. www. 3086−3090. [58] Y. 428.. Stanislav. G. 2013. Patrick. 3030−3034. Appl. Solid State Commun. 220−225. [57] R. Y. 3492−3494. H. Olga. 1998. C.. S. X. Struc. Z. [61] S. Yin. Uda.. J. Rimman. 2007.. C. Z. C: Cryst. T. CrystEngComm. S. 13. Wan. T. and Y. P. Frohlich. S. Fu. Wang. J. F. L. L. T. Lv.

R. large size and excellent optical properties were prepared by physical vapor transport method. China ABSTRACT Tetracene or pentacene -doped trans-1. high doping ratio.36. These doped crystals maintain the ordered layer structures and the crystal surface continuities. Chapter 3 DOPED ORGANIC CRYSTALS WITH HIGH EFFICIENCY. Northeast Petroleum University. which are verified by X-ray diffraction (XRD) and atomic force microscopy (AFM) analysis. Northeast Petroleum University. 199 Fazhan Road. Further. Efficient energy transfer from the host trans-DSB molecules to the guest molecules and the suppressing of the interaction among the guest molecules lead to color-tunable emission and high luminescent efficiencies. P.4-Distyrylbenzene (trans- DSB) crystals with high crystalline quality.37) has been obtained by controlling an appropriate mol ratio of guest to host (tetracene: pentacene: trans-DSB= 1: 1.  Corresponding author: Huan Wang. Daqing. Inc. the white-emission tetracene and pentacene -doped trans-DSB crystal with the CIE coordinate (0. COLOR-TUNABLE EMISSION TOWARD LASER APPLICATION Yang Zhao and Huan Wang College of Chemistry and Chemical Engineering.com In: Crystals and Crystal Growth ISBN: 978-1-63463-791-6 Editor: Wilfred Carter © 2015 Nova Science Publishers.35: 23.free ebooks ==> www.com . College of Chemistry and Chemical Engineering. Daqing 163318 P.com. E-mail: wanghuan83214@gmail.ebook777.1). www. R. 0. China.ebook777.

and iii) the additional losses due to the injected charges referred to as polarons and triplet formation [10]. the superiorities of organic crystals such as high thermal stability. The low mobility makes it hard to achieve high current densities. Hence higher mobility helps with each of these issues. [7] observed gain narrowing from the optically pumped thin-film waveguide. INTRODUCTION Organic single crystals constructed by π-conjugated molecules have attracted great attention in the field of organic optoelectronic materials [1]. which provides a model to investigate the basic interactions between the molecules (supramolecular interaction). Subsequently. electroluminescence [5]. In the meanwhile.ebook777. All three main issues outlined above relate to the low mobility of organic semiconductors. Despite success in optically pumped lasing. and the relationship between molecular stacking modes and optoelectronic performance (luminescence and carrier mobility) [2]. The solid state organic lasers have been demonstrated clearly by some groups. It also means that losses due to absorption of the contacts cannot simply be resolved by making the light-emitting layer much thicker so that the electric field of the guided mode has little overlap with the contacts. high ordered structure and high carrier mobility make them attractive candidates for optoelectronic devices such as optically pumped lasers [3]. In fact. field-effect transistors [4]. [8] made the first vertical microcavity laser based on conjugated polymers as gain materials. Typically.free ebooks ==> www. N. F. The academic motivation for organic single crystal research is their definite structures. There are three main issues to be considered relating to the feasibility of electrically pumped organic semiconductor lasers: i) the required current densities. Hide et al. The high concentration of polarons is due to their low mobility. optically pumped laser action has been demonstrated in a broad range of conjugated polymers and oligomers [9]. OLED materials development has evolved in a different direction toward amorphous materials because they are less prone to recrystallization and less susceptible to intermolecular interactions. ii) the additional losses due to the contacts. and photovoltaic cell [6].com 54 Yang Zhao and Huan Wang The primary results of optically pumped laser experiment indicate that these crystals have the potential application for organic laser diodes. the electrically pumped ‗injection laser‘ remains a significant challenge. . so recent reports of a polyfluorene- based material with mobility of 10-2 cm2/Vs are encouraging [11]. which can quench luminescence. Tessler et al.

we successfully dope a certain quantity of tetracene or pentacene (doping ratios approximate to 10%) into trans-1. achieving desirable light-emission doped crystal is significant towards laser application because high carrier mobility is regarded as the inherent characteristics compared with the amorphism. Doped organic molecular crystals have been paid much attention as early as 1970‘s and stimulated emissions in some systems were observed in succession [14]. high luminescent efficiency (65±4% for the undoped trans-DSB. and secondly their thicknesses (usually 1~10 µm).ebook777. and maintain the structural orderings of doped crystals as proved by X-ray diffraction (XRD) and atomic force microscopy (AFM) analysis. in which lack of structural definition and smaller size limited the application in optoelectronic devices. Thus. pentacene. But most of them were based on micro. the organic crystals combining efficient light emission and high charge-carrier mobility could be suitable as the candidates for electrically driven organic lasers because firstly their inherent long-range structural ordering could effectively avoid excitons annihilations that causing the sharp decrease of luminescence quantum efficiency under the high current densities [12]. Based on the principle of structural comparability (including molecular structures and their stacking modes) and spectrum overlap between the host and guest (ensuring efficient energy transfer). As we know.com Doped Organic Crystals with High Efficiency … 55 Consequently. 74±4% for the tetracene-doped trans-DSB. benefit to move the light-emitting active layer far away from the loss regions contacted with the metal electrode in the vertical diode structure. These doped crystals have large sizes (several millimeters). For the traditional organic optoelectronic polycene materials such as tetracene. Further in-depth photophysical characterizations of doped systems revealed the relationships between basic optoelectronic functions and molecular structures [15].free ebooks ==> www.ebook777. Physical vapor transport (PVT) method is the common one to obtain high-quality and large-size organic single crystal [16].4-Distyrylbenzene (trans- DSB) crystal by PVT method. doping dye molecules into certain host materials is a general method to increase the luminescent efficiency of the guest molecules for the organic amorphous materials [13]. This might be due to the lattice mismatch and the weak intermolecular interactions in organic crystals resulting in the difficulty of large-size doped crystal growth.or nano-crystals due to crystal growth method selected. Another merit of doping is that it can shift the emission away from the absorption region of the host to decrease the absorption loss of lasers.com . and 28±4% for the pentacene-doped trans- www. much larger than most of spin-coated and vacuum-deposited films‘. it is difficult to get high-luminescence-efficiency crystals and their crystals are hardly applied in electroluminescence or lasers.

1c is the tetracene-doped trans-DSB crystal (tetracene: trans-DSB=1: 14. Step-like morphologies have been found.1. which show the potential application of light-emitting transistors. The molecular structures of trans-DSB. MORPHOLOGY AND STRUCTURE OF THE CRYSTALS Figure 2a-c shows the AFM height images at the edge areas of the trans- DSB.free ebooks ==> www. respectively.1. pentacene. As shown in Figure 1b-d. (b) The pure undoped trans-DSB crystal. (d) Pentacene-doped trans-DSB crystal (pentacene: trans- DSB=1: 13. mol ratio). tetracene-doped trans-DSB and pentacene-doped trans-DSB crystals are observed. The spectra narrowings caused by amplified spontaneous emission (ASE) from the undoped trans-DSB.com 56 Yang Zhao and Huan Wang DSB crystals) and color-tunable emission (blue for the undoped trans-DSB. green and red emissions from the three crystals are observed. smooth surface and large size of several millimeters. The three crystals have the slice shape.7. mol ratio) photographs under the ultraviolet lamp.ebook777. Blue. diodes and lasers. tetracene. tetracene and pentacene are shown in Figure 1a. tetracene-doped trans-DSB and pentacene-doped trans-DSB crystals. Figure 1. which indicates that the self-waveguided emission occurs in the crystals. mol ratio). 1b is the pure undoped trans-DSB crystal. The emissions from the edges of the crystals are stronger than that from the body surfaces. . and 1d is the pentacene-doped trans-DSB crystal (pentacene: trans- DSB=1: 13. green for the tetracene-doped trans-DSB and red for the pentacene-doped trans-DSB crystals). (a) The molecular structures of trans-DSB.7. mol ratio). (c) Tetracene-doped trans-DSB crystal (tetracene: trans- DSB=1: 14.

43 Å) of trans-DSB molecules along ab-plane direction.70 Å.2 nm smaller than AFM results. the baselines of the XRD patterns are straight and the diffraction peaks are very sharp. c=34.74 1. Comparing the lattice constant with the XRD results. the diffraction peaks occur equidistantly with angle degree varying.72 1. respectively. Possible herringbone arrangement of trans-DSB molecules in crystal was recognized in previous work [18]. The values are summarized in Table 1.free ebooks ==> www. www.91 nm. respectively. The calculated layer thickness corresponded well with the step height observed by AFM. so these slice crystals should have the good ordered layer structures. and of the tetracene-doped trans-DSB crystal and pentacene-doped trans-DSB crystal are all along ab-plane.15) 1.15 in parentheses represents statistic zone. which correspond to the one-step height of these crystals in AFM image. which indicate that the ab-plane is parallel to the crystal surface of trans-DSB. the directions of intermolecular π-π stacking of the undoped trans-DSB crystal.ebook777.75nm. Figure 2d shows the diffraction patterns of Wide-angle X-ray diffraction (XRD) on the slice crystals.15) a Step heights from cross-section analyses in different regions of crystal surface exist slightly differences and the values listing in the table is the statistic average.74 and 1.75 (nm)/XRD Step height (nm)/AFMa 1. Summaries of the molecular layer thicknesses and step heights of undoped and doped crystals through XRD and AFM analyses Tetracene- Pentacene-doped Crystal trans-DSB doped trans- trans-DSB DSB Layer thickness 1.com . the average heights of steps observed on the three crystal surfaces are about 1. Table 1. b=7.98 nm.87 Å.72. we notice that the primary diffraction spacing of trans-DSB crystal is approximately identical to the monolayer height (c/2= 17. According to the Bragg equation the thicknesses of one molecular layer of trans-DSB.93 nm and 1. 1.93 (±0. As can be seen. 1. but generally ~0.ebook777. The step heights of undoped and doped crystals are nearly not different.15) 1. The value ±0. Also.98 (±0. The lattice parameters of trans-DSB were reported by Wu et al.87 Å.com Doped Organic Crystals with High Efficiency … 57 From the cross-section analyses. tetracene-doped trans-DSB and pentacene-doped trans-DSB crystals are calculated to be 1. due to systematic error brought by instrument existing in the process of scanning AFM images. based on the analysis of XRD patterns.91 (±0. [17]: a=5.

both trans-DSB as the host molecules and tetracene or pentacene as the guest molecules are all the linear configurations . (a) trans-DSB.ebook777. So the structural ordering of the host trans-DSB crystals has been retained after doping a certain quantity of tetracene or pentacene molecules into them. which is beneficial for different intermolecular combination in the crystal formation process and structural ordering maintenance. (c) pentacene-doped trans- DSB slice crystal surface AFM height images. The results of AFM morphologies and X-ray diffraction patterns suggest that all the crystals (undoped and doped) have the layer-by-layer structure and each layer corresponds to a molecular monolayer. Doping tetracene or pentacene into trans-DSB crystal leads the layer space to a little larger. (b) tetracene-doped trans-DSB. (d) XRD patterns of trans-DSB crystal. In our doped system.com 58 Yang Zhao and Huan Wang Figure 2. which may be due to the disturbance of the intrinsic trans-DSB crystal lattices caused by the embedment of doped molecules. tetracene-doped trans-DSB crystal and pentacene-doped trans-DSB crystal. Structural comparability of the host and guest molecules is an important precondition for realizing the successful growth of heavy doping and large size crystal by PVT method.free ebooks ==> www.

Further. The PL spectra of tetracene-doped trans-DSB crystal shows that the emission mainly comes from the tetracene molecules verifying the energy transfer. The similar phenomenon is also observed in the pentacene-doped trans-DSB crystal. Table 2.ebook777. OPTICAL PROPERTIES Figure 3a shows the absorption spectra of trans-DSB crystal. where edge-to-face arene-arene interactions are much stronger than intermolecular interactions along c axis direction. in the doped crystal formation process.com Doped Organic Crystals with High Efficiency … 59 and the molecules in the crystals are arranged in similar configuration. which may be caused by the conjugated effect of tetracene with the surrounding trans-DSB molecules (The 0-1 transition emissions of tetracene solution and crystal are about 511 nm and 531 nm. A certain quantity of doped guest molecules may replace the locations of original host molecules in crystal lattice. as proved in previous work [19]. The emission wavelengths and quantum yields of these several undoped and doped crystals are summarized and listed in the Table 2.ebook777. and then combine with neighboring molecules through intermolecular interaction to form an intact layer. namely ―herringbone‖ type structure in ab-plane. thus easy to form layer-by- layer structures. tetracene- doped trans-DSB crystal and pentacene-doped trans-DSB crystal. host and guest molecules could freely diffuse onto crystal surface from vapor.com . Figure 3b shows the emission spectra of trans-DSB crystal. Summaries of the emission wavelengths and quantum yields of some undoped and doped crystals Emission Wavelenght (nm) Crystal Quantum Yield 0-0 0-1 0-2 Trans-DSB 444 467 500 65±4% Tetracene-doped trans-DSB 497 531 572 74±4% Pentacene-doped trans-DSB 603 654 – 28±4% www.free ebooks ==> www. The emission peaks of tetracene molecules in the doped crystals have about 20 nm red shifts relative to that of tetracene molecules in solution. respectively). tetracene-doped trans-DSB crystal and pentacene-doped trans-DSB crystal. The tetracene or pentacene -doped crystals display the similar absorption consistent with that of undoped crystal that nearly comes from host trans-DSB crystal.

as shown in Figure 4. tetracene-doped trans-DSB crystal and pentacene-doped trans-DSB crystal. which favor the application in laser. the emissions from the edges are stronger than those from the body surfaces. (a) The absorption spectra of trans-DSB crystal. And the mol ratios of pentacene to trans-DSB in the crystals shown in Figure 1d (deep-red emission) and Figure 4c (light-red emission) are approximate 1:13. The herringbone arrangement of tetracene and pentacene molecules in the solid-state can quench the luminescence sharply. so their luminescent efficiencies in aggregated state are no more than 1%.7 and 1:33. respectively. respectively. the mol ratios of tetracene to trans-DSB in the crystals shown in Figure 1c (green emission) and Figure 4a (sky-blue emission) are approximate 1:14.free ebooks ==> www. By controlling the doped content of tetracene or pentacene molecules in trans-DSB crystals. respectively. .1 and 1:27.8. (b) The emission spectra of trans-DSB crystal. The respective ratios of guest molecules to host molecules in different color emission crystals could be estimated by chromatograph analysis. The absorption and emission separation of doped crystals will be advantageous in the lasers due to effectively decreasing the loss brought from self-absorption.com 60 Yang Zhao and Huan Wang Figure 3.ebook777. But doping tetracene or pentacene into a host crystal could effectively avoid the intermolecular aggregates. several crystals with different color emission are obtained. tetracene-doped trans-DSB crystal and pentacene-doped trans-DSB crystal. For example. From the photographs of these doped crystals. The crystalline-state PL efficiencies of the tetracene-doped trans-DSB and pentacene-doped trans-DSB crystals are as high as 74±4% and 28±4%.

we realize the blue. and the www. This is because when the growth-zone temperature is higher. the bigger the ratio of guest molecules to the host molecules is. In the optically pumped laser experiment the slice crystals are glued on the surface of the quartz substrates. while induces the decrease of the host emission. and the worse the quality of the crystals is. The photographs of tetracene-doped trans-DSB crystals with different color emission (a. Under the ultraviolet lamp. the disturbance of host-crystals lattice is more intense inducing the guest molecules to be more easily embedded into the host-crystals. pentacene-doped trans-DSB crystals with different color emission (c. The higher the growth-zone temperature is.ebook777.com Doped Organic Crystals with High Efficiency … 61 Figure 4.free ebooks ==> www. Due to the strong intermolecular aggregates. which indicates that the self- waveguided emission occurs. With the increase of the doped content of tetracene or pentacene molecules the energy transfer from the host to the guest increases.ebook777. green and red amplified spontaneous emission (ASE) from the organic crystals by the doping method. the emissions from the edges of all tested crystals are stronger than that from the body surface. b). It is found that the ratio of guest molecules to the host molecules is mainly influenced by the growth-zone temperature. pure tetracene and pentacene crystals show very low luminescent efficiencies (no more than 1%). Waveguided propagation of the emission is thought to be one prerequisite for lasing.com . Here. d) under the ultraviolet lamp. AMPLIFIED SPONTANEOUS EMISSION EXPERIMENT Doping of organic amorphous films with dye molecules has been widely utilized to tune the emission wavelength and reduce the lasing threshold by shifting the emission to longer wavelengths where the residual absorption is smaller [20].

green (531 nm) and red (660 nm) ASEs spectra of undoped trans-DSB. the emission peak intensities nonlinearly grow. the quantum yield is as high as up to 65±4%.free ebooks ==> www. . tetracene-doped trans-DSB and pentacene-doped trans-DSB crystals. as proved in previous work [18b]. However. Figure 5. The fluorescence quantum yield is not only determined by the radiative rate. PL quantum efficiency. minimum FWHM and threshold defined of undoped or doped crystals have been summarized in the Table 3. the FWHMs of the peak at 531 nm (0-1 transition) change from 18 nm at 2. which indicated the narrowing is caused by gain. This is because the trans-DSB crystal has low defect concentrations. accompanied by the narrowing of the emission spectra. but also by the emissive traps in the condensed phase. The ASEs spectra of undoped trans-DSB.com 62 Yang Zhao and Huan Wang ASE phenomena of them have never been reported. which is mainly ascribed to the suppressing of the interaction among the doped molecules. When the incident laser fluence is increased. The ASEs from the pure trans-DSB. the doped trans-DSB crystals with tetracene or pentacene present high luminescent efficiencies and the ASEs from tetracene or pentacene in the doped crystals can be observed. tetracene and pentacene -doped trans-DSB crystals are all occurs at the emission of 0-1 transition.4 µJ/pulse to 4 nm at 120 µJ/pulse and the threshold for the ASE is about 12 µJ/pulse from the non-linear variation of the peak intensity with the pump energy increasing. tetracene- doped trans-DSB and pentacene-doped trans-DSB crystals.narrowing. namely ASE. Figure 5 shows the blue (467 nm). which suggests that the 0-1 transition has the highest gain and the self absorption causes the relatively lower gain of 0-0 transition.ebook777. For tetracene-doped trans-DSB crystal. Although trans-DSB crystallizes in a herringbone arrangement.

33.35: 23.5 No No 60 352 WHITE-LIGHT EMISSIVE DOPED CRYSTAL AND TIME-RESOLVED PROPERTIES By optimizing the crystal growth conditions a series of doubly doped white-emission crystals (tetracene and pentacene -doped trans-DSB) with the Commission International del‘Eclairage (CIE) coordinates approaching to an ideal white light (0. However. doped trans- DSB DSB DSB PL QE 65±4% <1% <1% 74±4% 28±4% Min.1. 0. mol ratio) decreases to 0. Min.4 Threshold (KW/cm2) 48.36.com . FWHM (nm) 4 nm No No 4 nm 4 nm (µJ/pulse) 9.11 ns. Pentacene- Trans- Crystals Tetracene Pentacene doped trans. The decay time of the donor trans-DSB in tetracene- doped trans-DSB crystals with two different mol ratios (tetracene: trans- DSB= 1: 33. 1: 18).free ebooks ==> www. That means not only the existence of energy transfer from the donor trans-DSB to the acceptor tetracene. Figures 6b and 6c show the CIE coordinates of (0. 0. respectively.1. Figure 7a shows the PL decay curves of tetracene-doped trans-DSB crystals with different mol ratios (tetracene: trans-DSB= 1: 33.35: 23. PL quantum efficiency (QE).com Doped Organic Crystals with High Efficiency … 63 Table 3.35: 23. FWHM and threshold of ASE for different organic crystals Tetracene. Figure 7b shows the PL decay curves of tetracene-doped trans-DSB crystals with different mol ratios (tetracene: trans- DSB= 1: 33. determined by chromatograph analysis) in Figure 6a. 1: 18) are 1. but also from trans-DSB to the acceptor pentacene in the white-emission doped crystal. mol ratio) monitored at the emission wavelength of 444 nm. where the mol ratio of tetracene to trans-DSB (1: 23.04 ns.37) and photoluminescence (PL) spectrum corresponding to the tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1. and the white-emission tetracene and pentacene -doped www.33) were obtained (Figures 6a).1) is in between 1: 33 and 1: 18.1.ebook777.7 No No 12 70.49 ns and 1. 1: 18). and the white-emission tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.ebook777. the decay time of the donor trans-DSB in the white-emission tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.

(a) Photograph of white-emission tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.92 ns and 8. mol ratio) decreases to 2. mol ratio) monitored at the emission wavelength of 531 nm. 1: 16). 1: 16). Figure 7c shows the PL decay curves of pentacene-doped trans-DSB crystals with different mol ratios (pentacene: trans-DSB= 1: 28.35: 23. (c) PL spectrum of the tetracene and pentacene -doped trans-DSB crystal (λex = 400 nm). However. Figure 6.35: 23. 0.37) corresponding to the emission of the crystal.com 64 Yang Zhao and Huan Wang trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.35: 23. That indicates the efficient energy transfer from tetracene to pentacene exists in the white-emission doped crystal. the decay time of the acceptor tetracene in the white-emission tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.1. (b) CIE chromaticity diagram marked as a cross (0.06 ns between the ones (6. 1: 18) are 10.35: 23. mol ratio) under the irradiation of ultraviolet lamp (365 nm). respectively.51 ns.01 ns and 14.1. The decay time of the acceptor tetracene in tetracene-doped trans-DSB crystals with two different mol ratios (tetracene: trans-DSB= 1: 33.free ebooks ==> www.ebook777. and the white-emission tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.1. .1.37 ns. mol ratio) monitored at the emission wavelength of 608 nm.29 ns) of pentacene-doped trans-DSB crystals with two different mol ratios (pentacene: trans-DSB= 1: 28. The decay time of the acceptor pentacene in the white-emission doped crystal is 8.36.

ebook777. A summary of transient PL decay time for the above systems is given in Table 4.ebook777.com Doped Organic Crystals with High Efficiency … 65 This indicates the decay time of pentacene molecules in doped crystals is proportional to its doping concentration.free ebooks ==> www. a b Figure 7. but also from tetracene to pentacene in the white-emission tetracene and pentacene -doped trans-DSB crystal. there are the energy transfer not only from trans-DSB to tetracene and pentacene. Based on the above analyses. (Continued). www.com .

(c) λem =608 nm. 1: 16). mol ratio) crystals monitored at different emission wavelengths: (a) λem =444 nm. pentacene-doped trans-DSB with different mol ratios (pentacene: trans-DSB= 1: 28. Pure trans-DSB.37) has been obtained by controlling an appropriate mol ratio of guest to host (tetracene: pentacene: trans-DSB= 1: . the white-emission tetracene and pentacene -doped trans-DSB crystal with the CIE coordinate (0. large-size and high-quality doped organic crystals are obtained.36. (b) λem =531 nm. green and red emission. Further. tetracene and pentacene -doped trans-DSB crystals show the blue. respectively. The structural comparability of host and guest molecules is an important factor in the doped crystal growth.1.ebook777. Efficient energy transfer exists in doped crystals verified by steady-state and time-resolved fluorescence spectroscopy. CONCLUSION The physical vapor transport method is verified to get the doped organic crystals effectively and several color-tunable. 1: 18).35: 23. specially for the ones with large size and heavy doping.com 66 Yang Zhao and Huan Wang c Figure 7. 0. Time-resolved fluorescences of tetracene-doped trans-DSB with different mol ratios (tetracene: trans-DSB= 1: 33.free ebooks ==> www. The black solid lines show the decay curves of IRF- 379. and white-emission tetracene and pentacene -doped trans-DSB (tetracene: pentacene: trans-DSB= 1: 1. The results of XRD and AFM indicate that the ordered layer structure and thin film surface continuity of the host crystals have been maintained after doping a certain quantity of tetracene or pentacene into them.

91 DSB crystal (1: 33) 13.47 Tetracene-doped trans.1) 8.28 36.50 65.33 -doped trans-DSB crystal (tetracene: 7.1) in which the energy transfer exist not only from trans-DSB to tetracene and pentacene.20 DSB crystal (1:18) 14. 1.110 28.93 1. 1.79 2.ebook777.ebook777. and pentacene-doped trans-DSB crystals with different mol ratios (pentacene: trans-DSB= 1: 28.29 100 8.35: 23.92 DSB crystal (1: 28) 608 nm Pentacene-doped trans- 8.06 608 nm 2. but also from tetracene to pentacene. The primary results of optically pumped laser experiment indicate that these crystals have the potential application for organic laser diodes.06 100 8.23 71.04 444 nm 0.09 97.11 444 nm 0. 1: 16) at the emission wavelengths of 444 nm.1.61 1: 1. 531 nm and 608 nm Mean Decay Percenta λem Crystal lifetime τ time τ (ns) ge (%) (nm) (ns) 0.29 DSB crystal (1: 16) www.94 34.49 444 nm Tetracene-doped trans. tetracene-doped trans-DSB crystals with different mol ratios (tetracene: trans-DSB= 1: 33.09 1.35: 23.35: 23.30 23.86 76.37 531 nm pentacene: trans-DSB= 0.01 531 nm 2.free ebooks ==> www.51 100 14.07 10.39 2.67 Tetracene and pentacene 0. 1: 18). Decay data of the white-emission tetracene and pentacene -doped trans-DSB crystal (tetracene: pentacene: trans-DSB= 1: 1.04 63. Table 4.com .92 100 6. mol ratio).51 531 nm Pentacene-doped trans- 6.com Doped Organic Crystals with High Efficiency … 67 1.

14152-14153. R. 695-697. d) Reufer. C. Y. Mater. 3262-3264. Liu.. Hotta. 329-333. H. Bao. Funct. I. Lemmer. 38. D. Tung.. C. Soc. c) Moll. 913-917.. Samuel. D. Ramirez. 2004. U. Korshunov. S. 128. 303. V. 213-217. [9] Tessler. M.. V. Chem. Adv. Xu. Phys.. W. Forberich. V. 553-555.. 1644- 1646. 1997. R... Bradley. T. Schneider. L. Nat. Tartakovskii.. J. D... J. Haritani. Bao.. S. W. A. Mater. b) Briseno. M. V. W. M. Solid State Commun. 14. B. [6] Tseng. Kozlov. Yang..... E. M. 15. Ma. L. R. 91-97. S. 80. 2008. B. W. Delysee.. E.. L. Díaz-García. Podzorov. Hibino. N. G. K. Feldmann. Riechel. b) Ichikawa.. 127.. Adv. Phys. G. Mater. Khalfin. C.. B. G. J.. L. R. Mahrt. b) Xie.. M.. Cryst.. 20. Menard. M. T. T. Phys. J. Schnabel. P. R. F. D. A. P. [5] Hisao. I. G. R. 2002. V. L.. T.. 9... Kowalsky.. Hanif. 1452-1455. G. P. D. H. A. Ohara. Y.. F. Lett. Q.. Lavrushko. P. Andrew. e) Heliotis. S. Takayuki. Ma. 2007. Mangnante... Chem. M. Mol. 1178-1181. D. Willett. Science 2004. Yang. Appl. Nature 1996.. V.ebook777. Chem. Lett. Y. R. I. L.. M.. Broude.. Morikawa. 382. 29. Denton. Y. Xia. M. 2042-2043... 1974. Heeger. Reese. Chem.. Scherf... 444. N. Roberts. K. Adv.. b) Bulovic. Forrest. Turnbull. B. 13. [2] Reese. Gombert. M.com 68 Yang Zhao and Huan Wang REFERENCES [1] Pope. V. A. 435- 438. Koyama. 1963. N. Benderskii. M.. Yang. J. Bauer. Lupton. 16. 11. V.. Adv.. S. J. Y.. Someya. [8] Tessler. O.. Y. F.. [10] Samuel. S. D. . Z.. Y. Hotta. C... Appl. Campoy-Quiles. 431-434. 1833-1836. K.. Andersson. c) Fichou. Pei. 273. Mannsfeld.. Rogers. Mater. M. 2003... Barnes. C. D. [7] Hide. 2008. N. Cryst. Turnbull.. 1272-1295.. Brikenstein. 376-380. 7. Q. 2004. 2003.. J.. Wittwer. F. Appl. S. J. Kley. Chan.. Chi. R. 2006. A.. Bradley. 107. 2002.. R. Xia. J.. Schwartz. I. C. A. A. A.. 1999.. Wudl. J. Mater. E. Liu. N... Zaumseil. E. P. M. Yang. Z. T. 81. Giessen. 2005. [11] Yap.. M. 279.. Ling.free ebooks ==> www. U. D... 165-174... B. Liq. J. Dobbertin.. J.... Liu... V... 2001. G. G... Kallmann. U.. H. Nunzi. [3] Yanagi. Science 1996.. d) Butko..... Rev.. A. b) Avanesjan. T.. M. R.. [4] Sundar. C. 734-736. Tseng.. Lett. Adv. V... D. Nature 2006. Friend. Mater. B. J. 363-370. V. I. N. Am. 84. G. G. H. S. A.. T. S. R. Stavrinou. Phys. G. Scherf.. L.. Li. B. 1512- 1514. Inoue.. Mater. X. L. C. Mater. Z. Benstem. Taniguchi. Adv. Ye. Gershenson. Science 1998.. D. Cheng. H. D.

M. B 1998.. A. Mater.. D. Mater. S. Filippov. Yahiro. Peng. K. Wiley-VCH 2007. J. 8.. J. C.. E.. Phys. G. Graswinckel. J. Quantum. Rev. Sov. Mater. J. 221- 227. Benderskii. 2008. 4. G. b) Gierschner. Gierschner. Simpkins. Meekes. H. H. L. Blakely. D. Egelhaaf.. Fu.. 12.. Yang. Chen. Siegrist.. P. A. S. Adv. Iwasa1. 37-44. Milián Medina. b) Ruiz. Lavrushko. H. S. Steinhuber. P. Takahashi.. P. Ehni. Clancy. J. Oelkrug. D. 79-83.-J. Electron 1978. VanSlyke. D. S. Egelhaaf. 137.... H.. R. C. Cryst. b) Avanesyan.. Gierschner. J.com Doped Organic Crystals with High Efficiency … 69 [12] Takenobu. Ogurtsova.. A. C. H. K... J.... Y. J. Phys. Phys. Vardeny.. M. [15] Egelhaaf. V.. Organic Molecular Solids. Malliaras. Müllen. Chem. W. 2003. Bisri. Lett. L. Phys. N..ebook777. 066601. Iannotta. T. M. R.. Y. 2004. G... Growth Des. P. 30.. 127. Appl. C. M. 102. Chem. (a) 1975. C. Z. [20] McGehee. W. Hohloch.... 187. Met. Met.. J. J. Headrick. Adv. Ann. Tompert. G. Toccoli. F.. R. 449-454. T. V. 1655-1668...... Heeger. C. J.. 65. H.... Phys. C. C. Malkes. H. Cryst.. V. [16] Laudise. L. Y.. [17] Wu.. Oelkrug.. 2008. Sol. H. A. Beljonne. H. 217-243.. Adachi.. 123. [13] Tang. B. C. A.. M..free ebooks ==> www. A. K.. 16. B. Z. C. 2005. Choudhary.-J.. A. S.. F. 2004. 100.-J. 144914.. Kloc.. Delong. Fluorescence 1998. 1989. [14] Naboikin. V. D. Growth 1998. S. 4497-4508..com . A. b) Gierschner. J. Stat. Chang. Phys. M. 1902-1907. J.. Ferraris. A. Chem. M. d) Zhao. Y.-J. J. Synth. Wolf. 8. [19] Cuppen. S. G. 1351-1357. www. 2000.. P.ebook777. 457-461. T. M. Hanack. 57. D. W.. 2002. H. Brikenshtein. B. C... c) Oelkrug. Podgornyi. Mayer. Yao. 2006.. C. Bazan.. 3610-3616. G. H. D. Nickel. M. c) Schwoerer. Chem. Synth. T. 781-789. [18] Spano. Benmansour. Egelhaaf. Rev. Q. 939-941. Hu. A. 20.

Furthermore. a hypothetical approach is presented to enable evaluating the effect of macromolecular additives on the occurrence of needle-like crystals. AlQadmous. Syria ABSTRACT This chapter represents specific review on the effects of impurities on the growth from solution. Kubota-Mullin model as adsorption model describing the effect of the shape. Syria. Inc. Tartous. Khaddour Faculty of Pharmacy. Further. P.com . Email: issamoali99@gmail. Tartus. Finally. and discussed for the specific cases of sucrose grown from raffinose-doped solutions. Chapter 4 MODELING EFFECTS OF IMPURITIES ON CRYSTAL GROWTH Issam A. Banias. the size and the orientation of the impurity at the interface layer is reviewed. and deeply discussed.Box: (297). namely the birth and spread model.free ebooks ==> www. AlAndalus University. to understand the effects of impurities on the kinetics and the interfacial free energy of growth is also illustrated.com.O. www.  Phone: +963 953389614.ebook777.com In: Crystals and Crystal Growth ISBN: 978-1-63463-791-6 Editor: Wilfred Carter © 2015 Nova Science Publishers. benefiting of application of the 2D nucleation models.ebook777. The concept of the impurity partition coefficient and its importance to the recrystallization processes is explained.

therefore. INTRODUCTION When crystallizing a particular solute from solvent. Khaddour 1. their effect may still significant to be considered as impurities [1]. To date there have been two different approaches to clarify the effect of a solvent on crystal growth and morphology. Consequently. Generally. it has been proposed that preferential adsorption at specific faces will inhibit their growth as removal of bound solvent poses an additional energy barrier for continued growth [3. In the later it is usually named additives. at the steps. different orientations have varying affinities for the solvent. The crux of the matter is that a given crystallographic orientation on a crystal exposes a particular set of atoms of the solute molecule. In one theory. Then if the kink site adsorption is possible. and . Impurities can affect the solution structure changing by that the equilibrium concentration and hence the supersaturation. The selection of the solvent is important. More impurity would be needed if the step site adsorption is the case.free ebooks ==> www. The solvent from which the crystals are grown is. small-molecule additives. the presence of other dissolved solutes may profoundly affect the measured growth rates. by adsorbing selectively on certain faces of the crystal. Even if foreign solutes are present at low concentrations. These varying affinities impart different growth rates to the crystal faces and therefore influence the shape. the area of this face is expected to increase in relation to the areas of the other faces of the same crystal. additives (impurities) are divided into three categories: tailor-made additives. growth retardation could be affected at relatively very low impurity concentrations in the solution. an impurity. impurities may adsorb at the kinks. Furthermore. Further. favorable interactions between solute and solvent on specific faces lead to reduced interfacial free energy. or they are intentionally added. Alternatively. So. they alter the characteristics of the adsorption layer at the crystal-solution interface and influence the integration of growth units [5]. causing transition from smooth to rough interface and concomitant faster surface growth. in the strictest sense. because the nature of the solvent-solute interactions at the crystal surface greatly influences the equilibrium shape of the crystal. as a change of the solvent frequently results in a change of crystal habit as well as the growth of different faces [2]. 4]. or the observed crystalline habits. impurities (additives) can inherently be present in the crystallizing medium. when a growth is inhibited in a direction perpendicular to a given face.com 72 Issam A.ebook777. and higher impurity concentrations may be required if adsorption only occurs on a ledge or face site [6]. or at the ledges during the face growth.

ebook777. (K) is the absolute temperature. and their application on growth data. two models describing the effects of impurities on crystal growth are presented.ebook777. Both terms additives and impurities will be interchangeably used in this chapter. Further.com . practically identical. polymer. For > 1. and performing the recrystallization process will result in improvement in the purity of the crystalline product. For < 1. www. guides. (J/mol K) is the universal gas constant. and Δ (J/mol) is the change in the thermal entropy of the impurity caused by its transfer from the solution to the crystal. So. are shown and the results are discussed. The aim of this chapter is to provide some basics. the concept distribution coefficient of the impurity is explained and its importance is discussed. respectively.free ebooks ==> www. Tailor made-additive are ones that are structurally related. mainly for sucrose crystals. when = 1 the material will not be purified by repeated crystallizations. and are the activity coefficients of the impurity at its equilibrium (solubility) and actual concentrations in the solutions corresponding to concentrations and . assuming that the crystallizing solute has a molecular weight of no more than 200 . The equilibrium thermodynamic distribution coefficient (dimensionless) is usually defined as the ratio of concentration of impurity in the crystal divided by that in the solution [7]. ( ) (1) and are the actual concentration (in mole fraction) of impurity and solute in solution and and are the equilibrium (saturation) corresponding concentrations. Small molecule additives include surfactants and fatty acids. the impurity concentrates in the crystal. or peptide. Δ (J/mol) is the heat of solution of the impurity in the solid state. to the solute molecule. and notes on studying the effect impurities on crystallization kinetics for the growth from solution. the crystal–medium interface serves as a filter to impurity particles. But. DISTRIBUTION COEFFICIENT OF IMPURITY The term distribution coefficient is used to measure the degree of the incorporation of a certain impurity in the crystal. A macromolecular additive or impurity could be a protein.com Modeling Effects of Impurities on Crystal Growth 73 macromolecules.500 Daltons. 2.

ebook777. However. but at very slow growth rates. this model was not found to be particularly applicable to growth from solution. Further. the model predicts extremely highly purified (in essence 100% purity) crystals at vanishing or very slow growth rates [11].02. It is worth to mention that the increase of the dextran concentration from 1000 to 2000 ppm/Brix did not show remarkable change in the effective distribution coefficient. [12] used equation (2) to measure the dextran partition coefficient for sucrose crystallization in presence of 1:1 mixtures of two molecular fractions of dextran (75 and 250 kDa). as the impurity is accumulates at interface. from sucrose growth at 40 and 50 ºC. were respectively reported at the same supersaturations.com 74 Issam A. Hall [9] and Burton et al. Regarding that the volume diffusion is controlling the growth rate. On the other hand. and (m) is the boundary layer thickness.5 times higher values for the effective partition coefficient of dextran. They found that the effective partition coefficient of dextran. which is the ratio of impurity concentration in the crystal to its average concentration at the crystal-medium interface.40. crystals of better quality and larger sizes will be expected for the cases when >1 [7]. . and at different temperatures (30. so increasing the distribution coefficient value [8]. However. Khaddour In this regard. it could be beneficial to recrystallize sucrose to purify it from similar fractions of the dextran being incorporated in the sucrose crystals.free ebooks ==> www. see Figure 1.50 ºC). [10] suggested the following form to estimate the value of ( ) ( ⁄ ) (2) (m2/s) is the diffusion coefficient of the impurity species.1 Promraksa et al. with variable concentrations (1000 and 2000 ppm/Brix). at 30 ºC and variable supersaturations ( ). [10] proposed some forms for the as function of the normal growth rate (m/s) for the case of growth from melt. Sound measurement of incorporation of impurities requires estimation of the effective segregation coefficient . is almost constant and equal to 0. lower quality and smaller crystals will be produced when < 1. 4 . Although. The model is based upon the assumption of increased concentration of the impurity molecules in the boundary layer around the growing crystal due to partial rejection of impurities. They also found that the effectiveness of the dextran mixture increases with increase of the growth rate of sucrose. As conclusion. it is found that the structural similarity between the solute unit and the impurity unit enhances the incorporation of the impurity into the crystal. Burton et al.

Illustrative chart of the partition coefficient for dextran in sucrose crystallization at different temperatures (30. 50 ºC). (J/K) is the Boltzmann constant.ebook777. [12] 3. where (m) is the radius of a 2D critical nucleus: ( ) (3) (J/m2) denotes the solid-liquid interfacial free energy. MODELING IMPURITY EFFECTS An impurity is considered immobile when it exerts a pinning mechanism of the face growth. more specifically. whereby the progress of the growth layers on a crystal surface is blocked by individually adsorbed impurity species [13].ebook777. Adopted from Promraksa et al.free ebooks ==> www.com Modeling Effects of Impurities on Crystal Growth 75 Figure 1. For a spaced distance www. 40. the additive must have an adsorption lifetime much longer than the characteristic time for surface growth [4]. represented as function of relative supersaturation. Actually the term immobile impurity is relative.com . (m) is the size of the growth unit. A complete stoppage of growth would occur when the surface distance between the adsorbed impurity species (m) is less than .

Schematic illustration of the retardation effect of the surface-adsorbed impurities on the advancement of the steps. see Figure 2 [13]. Khaddour that step would pass between the impurity units.e. by impurities is related to the impurity concentration in solution through Langmuir adsorption isotherm [14. Figure 2. i. however. which is used to relate the lateral growth velocity in the presence of an impurity (m/s) to its counterpart for the growth from pure solution (m/s) [16].free ebooks ==> www. it is expected to continue to grow at lower rate than without any impurity present. Kubota-Mullin Model The early mathematical version of this model assumes that the blockage of the surface active sites. 3. and it is determined applying Langmuir isotherm as follows ⁄( ) (5) .1.com 76 Issam A. kink sites.. because of its curvature. ⁄ (4) where is the fractional surface coverage by the adsorbed impurity at equilibrium. 15]. Further improvement to this approach included the addition of the impurity effectiveness factor .ebook777.

If the linear growth rates (m/s). www. the relative growth rate decreases very rapidly with increasing reaching zero at very small values of .ebook777. ⁄ asymptotically. but when the growth rate never approaches zero even for .com . are proportional to the corresponding lateral growth velocities. and . when and then . from pure solution. For . [17] Figure 3 depicts the dependence of the relative growth rate ⁄ on the dimensionless impurity concentration at different values of the effectiveness factor. and (m/s).free ebooks ==> www. when . Relationships between the relative growth rate and the dimensionless impurity concentration for different values of the impurity effectiveness factor . from impure solution. results . Figure 3. However.com Modeling Effects of Impurities on Crystal Growth 77 where (mole fraction) denotes the concentration of the impurity in the solution and (dimensionless) is Langmuir constant.ebook777. then ⁄ ⁄( ) (6) Thus. When .

Equation (9) contains several variables where the solid-liquid interfacial free energy of the 2D nucleation is the most important. The author applied this model to estimate the influence of raffinose. and may be expressed in the form [7] ⁄ (7) where (m) is the average distance between the kink sites along the advancing step [4. Khaddour When adsorption of impurity occurs at kinks. This variable is mainly related to the orientation. the temperature and the supersaturation degree [21-23].ebook777. differential heat of adsorption (J/mol) can be estimated after the knowledge of the value of the Langmuir constant using the equation [7]: ( ⁄ ) (10) In general. development of Kubota-Mullin model was carried out on the basis of the Langmuir adsorption isotherm. size of the additive molecule. . on the advancement of the steps in the direction [010] at the face (100) for data published by Albon and Dunning [25]. as added impurity. or orientation of the impurity molecules (a stereochemical effect) [20]. see Figure 4.com 78 Issam A. where the differential heat of adsorption does not depend on the surface coverage [7]. However. for a certain material. decreases steadily with increasing of the adsorbed amount [24]. but also affected by the shape. . 18]. Further.free ebooks ==> www. The equivalent expression of Equation (6) is given as [19] ⁄ ⁄ (8) Then the effectiveness factor can be presented in the form [5] ⁄ ( ) (9) The introduction of the effectiveness factor enables evaluating the growth suppression characteristics of an impurity which are expected to depend on the size. shape. the linear coverage of the kink sites along the advancing steps by the adsorbed impurity units is equal to the fractional coverage of the surface .

3 0. They found. Table 1 shows higher step-advancement retardation effect of raffinose at lower supersaturations.5 KLci Figure 4.02 2 1. Table 1.56 0.57 Estimation of the effectiveness factors and the corresponding Langmuir constants. Results indicate that raffinose shows the effects of strong adsorbing impurity which effectively retards the growth rate at relatively low concentrations. presented in Table 1.013 0.9 0.015 0.2 0.013 0.8 355. Effectiveness factor.7 15.1 325 232. differential heat of adsorption and the maximum surface coverage ratio of raffinose obtained applying of Kubota-Mullin model for sucrose growth at different supersaturations and at 30 ºC Relative supersaturation Parameter 0. and at 30 ºC.45 1.5 1.5 1 1.0065 0.015 0.8 14.6 13.0065 0.57 0.51 0. ( ̅ ). [26] tested growth kinetics of ( ).com . ( ) and ( ̅ ̅ ) as the four most important F (flat) forms of sucrose crystal grown from pure solutions and from raffinose doped solutions. Relative step velocity on the [010] direction at the face (100) of the sucrose crystals grown in presence of variable concentrations of raffinose at different supersaturations.com Modeling Effects of Impurities on Crystal Growth 79 1 0.8 0.4 0.1 0 0 0.5 0. is reduced by 25% when supersaturation is doubled. applying www. Sgualdino et al. is performed using Solver in Excel application. Further.7 (max.6 vi /v 0.3 443. Langmuir constant.ebook777.ebook777.) 0.02 0.4 14.7 0.free ebooks ==> www.

Hence raffinose can markedly affect the growth kinetics through the reduction of the density of kinks available to the incorporation of the incoming sucrose molecules. and the one obtained by Kubota [20] at 30 ºC from analyzing Albon and Dunning data. Kubota Mullin model represented better the data than Cabrera Vermilyea model. However. the solution is only valid in its relative sense. and/or due to that the retarding effect of growth of raffinose on this face occurs only by adsorption at terraces. but the opposite occurred. when the retarding effect of raffinose is driven by kinks-adsorbed impurity mechanism. so they expected lower values of at 40 ºC than at 30 ºC. As the solution of the Kubota Mullin model is numerical. see Figure 5. Again the author believes that the reason lies in . In this course. The author believes that existence of a threshold concentration of raffinose ( ) for its effect on the growth of the form ( ̅ ̅ ) can be due to the relatively high adsorption energy of raffinose on this face. So.. but proper to explain the data. for the same data from Albon and Dunning [25] work. thereafter a dramatic increase in the interfacial free energy will result in. The author belives that. However. and mostly at similar probabilities. see Table 1. the growth inhibition effect takes place through changes in the step structure. and . the values of the real parameters can be different from the ones obtained by numerical solutions. However.ebook777. ( ) and ( ̅ ̅ ). So indicating that raffinose adsorbs mainly at the kink sites in the early stages of growth. will affect the values obtained by the numerical solution. that raffinose strongly hinders the growth rates of the forms ( ). Their interpretation includes that the adsorption process is an exothermic process. Sgualdino et al. so the change of the initially proposed limits of the targeted variables.com 80 Issam A.e. [26] and Kubota [20]. shows further discrepancy with both estimations of the by Sgualdino et al. i. ( ̅ ). the effect on mobility reduction of step ledges due to the raffinose molecules firmly incorporated on the surface terraces cannot be neglected. but for other faces the adsorption occurs mainly at kink sites. Fitting the data to Kubota-Mullin and Cabrera Vermilyea models shows that the resulted curves from both models are overlapping at the late stages of growth and a distinct discrepancy appear between these curves in the early stage of growth. but the later adsorption (second part of the growth curves) occurs at kinks and terraces simulataneously.free ebooks ==> www. The above- mentioned analysis by the author. Khaddour Kubota-Mullin model. [26] pointed out a contradiction between their value for from at 40 ºC. where lower values than those presented by Kubota are found. and the effects increases with increasing of added concentrations of raffinose. and much lower effectiveness factors were also estimated.

Figure 5. Sgualdino et al. Birth and Spread Model This model allows for both nucleation and subsequent step advancement at a finite rate. Schematic representation of relative growth rates of four forms of the sucrose crystal in presence of variable concentrations of raffinose at two different relative supersaturations (left: = 0. In fact. for obtaining a solution by Solver. [15]. www. and the galactose unit projecting out of the surface to inhibit subsequent growth. is selectively inhibited. Furthermore.2. where multiple nucleation and subsequent spread are depicted [27].com . Figure 6 shows the surface pattern of face (100) of the sucrose crystal grown from pure solutions. where values follow exponentially the changes in the . and right = 0.08. then changes of hundred thousand or million in values will not result any change of the set initial value of . because this corresponds to a molecular orientation in which raffinose can sit with its fructose component on the surface. In other words. when is set in advance at certain value. and similarly to Black et al. such insensitivity can be understood from Equation (10). [26] proposed that the growth of the (100) faces of the sucrose crystal. small changes in the heat of adsorption result in big variations in the Langmuir constant.ebook777. 3. So. in presence of raffinose.ebook777.04) and temperature of 40 ºC [26].com Modeling Effects of Impurities on Crystal Growth 81 the applied numerical method for estimating the and .free ebooks ==> www. to be insensitive to a very wide ranges of . For example the author found that the different and the repeated trials.

In effect. ⁄ [ ( ⁄ )] [ ⁄ ( )] (11) where (m/s) is a constant given by ⁄ ⁄ ⁄ ⁄ ( ⁄ ) ( ⁄ ) (12) . for pure and impure solutions can be a time dependent parameters.com 82 Issam A. see example in Figure 7. [21] applied birth and spread model to evaluate growth kinetics of sucrose in presence of variable concentrations of different molecular fractions of dextran at 40 and 50 . However. for that it is neglected in the application of birth and spread model for the impure systems. Khaddour et al. respectively. can be safely ignored as these are mainly a property of the face growth rate. the found dead supersaturation zones. the found dead zones. Such general enhancing effect was understood from applying birth and spread model. Atomic force microscopy images showing the occurrence of multiple 2D nucleation events for the growth of the face (100) of the sucrose crystal. The application of the birth and spread model is carried out using Equation (11). At 40 . In this regard. Khaddour Figure 6.ebook777. where multiple 2D nucleation mechanism is expected to dominate. Further. and not for the overall growth rate. birth and spread model was developed to evaluate growth from pure solutions. even when tailor-made additives are used at high concentrations.free ebooks ==> www. the various dextran fractions caused slight enhancing effects of the overall normal growth rates of sucrose.

so. [21] suggested that the lower interfacial free energies in the case of sucrose crystals grown from dextran-doped solutions. see Figure 9.ebook777. Dextrans are macromolecules. Khaddour et al. So. In fact. is due to the hydrocarbon parts of the glucose moieties of the dextran molecule. see Figure 8. Finally. see equation (11). where values are determined from the slope of the obtained equations from the fitting by linear regression type. (m2/s) is the surface diffusion coefficient of the adsorbed molecule.e. The interfacial ) free energy between the supersaturated solution and the crystal surface is then estimated using equation (13). reducing the value of the interfacial free energy. this assumption is very logical as if the hydroxyl groups will be projecting outwards from the dextran- targeted faces. 28-30].com .free ebooks ==> www. and (m-2) is the equilibrium concentration of the solute on the surface. In other words. 4 and 6 for one-. through causing about 20% reduction to the interfacial free energy of that for the pure system. or three-dimensional diffusion. Application of birth and spread model is to be done by graphing *( ⁄ [ ( )] )+ versus ( ( ). at 40 . such orientation achieves the maximum mutual interaction energy between molecules at the interface [24. the hypothesis of van Enckervort and van den Berg can be other aspect of the case of sucrose growth in the presence of different dextrans at 40 .. Further. they will enhance the solubility of sucrose by contributing formation of stronger hydrogen bonding net at the interface layer. and are the step and kink retardation factors. at 40 . then reducing the crystallization rate. (m/s) is the average speed of the surface adsorbed molecules.ebook777. as a result they mostly act like immobile impurities. two-. i. the impurities will promote rather than decrease the growth rate. in comparison with the pure system. the values of the kinetic coefficient is determined from the corresponding intercept. where is a constant that varies from 2. (m) is the mean diffusion distance of the solute on the surface during time (s). ⁄ (13) Table 2 shows that the different fractions of dextran. respectively. they project outwards from the dextran-targeted faces of the crystal. enhanced the overall linear growth rates of sucrose.com Modeling Effects of Impurities on Crystal Growth 83 where (m3) is the volume of the growth unit. van Enckervort and van den Berg [31] reported that when the interaction between the immobile impurity and the growth units is exceeding the bond energy between adjacent growth units. This assumption is also supported by the structural similarity between the dextran www. .

It is found that the added impurity increases the growth rate with increase in impurity concentration. Plausible reasoning of this discrepancy is that Kumar applied the BCF model to data represent the overall linear growth rate. at 50oC. and the other authors applied it to the growth of specific faces. Hodag CB6. Valčić [33] found a good agreement of his experimental results on sucrose growth from pure solutions. In other words. sharp decrease in the growth rate of sucrose. with the BCF surface diffusion model.28 g/L of water. dextran and sucrose molecules contain glucose units in their structures.1 m/s.28 g/L of water. imparting a promoting effect on the growth rate of sucrose. in the case of sucrose growth in presence of the dextran fractions 250000 and 2000000. Further.ebook777. so what determines the growth rate for the later run is the kinetic coefficient which is equal to 2.com 84 Issam A. it is found that the growth of sucrose is controlled by kinetic coefficients rather than by the interfacial free energy effect. Similarly.85 g/L of water in comparison with the run of the pure system. Khaddour and the sucrose. However. but poorly at 30 oC. see Figure 10. and the results showed that the interfacial free energy of growth decreases with increasing of the impurity concentration. Sgualdino et al. ( ) and ( ̅ ̅ ).. so the kinetics of growth of these faces is well described by the BCF model. and with the run of dextran concentration of 1. BCF model poorly represents the data well at 50 oC. on the growth kinetics of sucrose crystals at 30 and 50oC. Growth data were analyzed using birth and spread model. see Table 2. [26] reported that screw dislocation mechanism is dominating the growth at the faces ( ̅ ). and it represents less than half of the value of the kinetic coefficient for the pure system run.e.free ebooks ==> www. and about 60 % of the kinetic coefficient of the run performed with dextran concentration of 1. On the other hand. . i.85 g/L of water. was occurred for the run at concentration of dextran (dextran fraction of 70 kDa) of 3. Similarly Kumar [32] studied the effect of non-ionic surfactant.28 and 3. the added surfactant decreases the solubility of sucrose in the mixture. Practically the same interfacial free energy is found for the runs with dextran concentrations of 1. So. at 30oC.

102 and 0.ebook777.com . www. Examples of application of birth and spread model for sucrose growth from starting from two different initial supersaturations (0.free ebooks ==> www. where linear regression enables estimating the values of and .ebook777.com Modeling Effects of Impurities on Crystal Growth 85 Figure 7. Occurrence od dead supersaturation zone during growth of sucrose from pure solutions and in presence of dextran at 50 ºC [21].181). Figure 8.

at 40 and 50 . Interfacial free energies  and the kinetic coefficients of the growth of sucrose.85 .6 4.8 1. free ebooks ==> www.3 7.6 2.5 1.1 7.1 3.4 3.2 1. - .6 3.ebook777.3 3.28 4.1 3.1 70 3.71 4.8 7.28 3.0 1.5 1.2 2.1 2.85 4.71 3.71 3.5 3.0 2.71 4.3 2000 3.1 2.0 2.85 4.5 Dextran fraction (kDa) 1.com Table 2.2 250 3.6 4.3 2.1 2.71 3.28 4.0 2.28 3.7 7.85 4.85 3.1 2. from pure solutions and in the presence of different concentrations of the three used molecular weight fractions of dextran [21] Run 40 50 Dextran 2 Dextran ( J/m ) ( m/s) ( J/m2) ( m/s) g/L of water g/L of water Pure system 0 5.28 4.9 5.9 2.7 0 3.0 2.5 7.2 1.6 1.85 4.28 4.6 4.

with permission from the author.com Modeling Effects of Impurities on Crystal Growth 87 Figure 9. to the solution side.free ebooks ==> www. Hydrocarbon parts of glucose units of the dextran molecule projecting outwards. of a face-adsorbing dextran of a growing sucrose crystal. Plots of linear growth rate versus supersaturation ratio for different impurity concentrations: (top) at 30 oC and (down) at 50oC. www. Figure 10.ebook777.ebook777.com .

the ratio ⁄ is given by ⁄ (( )⁄ ) (16) and can be used to evaluate the relative importance of the attachment and the detachment fluxes. (J) is the chemical potential difference at the interface from the crystal–fluid equilibrium value. 35]. the degree of supersaturation is expected to be lowered at the surface points of the incorporation of the additive [34. and considering that the growth is limited to the direct integration mechanism. which directs the growth to other directions to satisfy the higher interaction energy condition. which decreases the incorporation of the solute molecules in directions normal to the alignment of the adsorbed macromolecule on the surface. Khaddour 4. In other words.ebook777.com 88 Issam A. the maximum interaction energy of orientation of the incorporating solute molecule is not achieved. Further. Further.free ebooks ==> www. When the solute molecule is attempting to be added in the vicinity of the alignment of the macromolecule on a macromolecule-targeted face. and in . So. The dissolution of the surface solute molecules occurs at rate that depends on the coordination. CRYSTAL ELONGATION DUE TO MACROMOLECULES ADDITIVES Considering that the face-specific adsorption of a macromolecule additive results in anisotropic spread of steps across the targeted face. the impinge rate at which the sucrose molecules impinge a square array of the face of the crystal can be given by the relation ( ⁄ ) (14) where is an overall frequency factor has the same unity of and includes any retardation of the attachment. [36] ( ⁄ ) (15) denotes the number of the nearest neighbours of the solute molecules and (J) is the bond energy between pair of such neighbours. thinner (elongated) crystals than could be predicted on the basis of the proportionality between the face growth rate and the attachment energy of a face slice will be produced.

Both of studied additives. So. and dependent on the kinetic coefficient in the other case. www. This chapter went beyond the scene trying to characterize the kinetics of the growth process in presence of additives. raffinose and dextran. in this chapter belong to the tailor- made class. The term ―additives‖ rather than the term ―impurities‖ is being in use nowadays.com Modeling Effects of Impurities on Crystal Growth 89 direction perpendicular to the alignment of the macromolecule. increase or decrease the number of the crystal faces. Raffinose effects on the concerned faces of sucrose appear to be driven by the interfacial free energy parameter. the addition of certain additive can alter the shape of the crystal. so reducing the growth rate at this direction. However.com . dextran effects were interfacial free energy dependent in one case.ebook777. as example. the quality and the properties of their final products. Both growth retarding or enhancing effects of the additives provide powerful tools to better engineered crystals depending on their applications. lower interaction energy and less number of neighbours at reduced chemical potential will prevail. in very intelligent way. Effectiveness factor introduced in Kubota-Mullin model represents necessary measure to evaluate the impact of the interfacial free energy of growth at constant supersaturations. or when it noticeably modifies the morphology of the growing crystal along the crystallographic direction parallel to the direction of the macromolecule alignment at the adsorption-targeted face.ebook777. CONCLUSION The development in crystal growth science enabled crystal engineers to supervise and control. that in comparison with similar crystal grown from pure system.free ebooks ==> www. This theoretical discussion applies only for the case where the macromolecule has a reducing effect on the growth rate. These findings enabled the development of theoretical interpretation of the formation of needle-like sucrose crystals in presence of macromolecules like dextran.

57. Crystal Shape Engineering.. Turnbull. [6] Davey. G. John Wiley & Sons: Chichester. Additives and Crystallization Processes. P.com 90 Issam A. L. Snyder. J. W. Mantovani. Prim. A. 2001. F. 2nd ed.. Leiserowitz. Journal of Crystal Growth 1976. B51. N. [2] Davey. Griffin. Mullin.. Doremus. Butterworth-Heinemann: Oxford. R. R. A. Prentice-Hall Inc.. habit. Industrial & Engineering Chemistry Research 2008. Vaccari. G. (14). 4th ed. 1973. [9] Hall.. D. 1987-1991. J.. Schneider.. B. (24).. R. M. Ed. D. On the relations between morphological and structural modifications in sucrose crystals grown in the presence of tailor-made additives: effects of mono. M. The Growth of Crystals from Solution.. L. [12] Promraksa. A. I. In Crystallization Technology Handbook. 1958. K.... [7] Sangwal. Whiting.. R. Materials Chemistry and Physics 2000.... Flood. (2-3). Segregation of impurities during the growth of germanium and silicon crystals Journal of Physical Chemistry 1953. Roberts. ed. The distribution of solute in crystals grown from the melt. Acta Cryst. Eds. A.ebook777. 109-119.. 1995. The effect of impurity adsorption on the kinetics of crystal growth from solution.. E.. D. 316-322. Lahav. growth.: New Jersey. J. W. Understanding and control of nucleation.. P. 2001. J.free ebooks ==> www. 21.. Tamburini. C. [8] Sgualdino. Measurement and analysis of the dextran partition coefficient in sucrose crystallization.. R. Journal of Crystal Growth 1982.. Sizemore. C. J. Crystallization. P. A. Quality of Crystalline Products. 66. ed. [11] Mersmann. Journal of Crystal Growth 2009. 58. Vermilyea. E. J.. [10] Burton... (2). M.. 34. 936-839..and oligosaccharides. M. R. Reid. 115-148. 3667-3673. W. 304-312.. Popovitz-Biro.. Browning.... R.. Wiley & Sons: New York. J. C. 47. [3] Weissbuch. 2007. Mersmann. [13] Cabrera. Slichter. 9812-9833. R. dissolution and structure of two. A. Modeling Crystal Growth Rates from Solurtion ed. Marcel Dekker: New York. G... M.. . R. Journal of Chemical Physics 1953.. W. Doherty.. [4] Lovette. A.and three-dimensional crystals using `tailor-made' auxiliaries. D. N. Habit modification of succinic acid crystals grown from different solvents. 311. Khaddour REFERENCES [1] Ohara.. In Growth and Perfection of Crystals.. A. [5] Mullin. Aquilano.

I. Part 2). Physical Chemistry of Surfaces 6th ed. J. Metastable zone width for secondary nucleation and secondary nucleation inside the metastable zone. Ferreira.. Rocha. [22] Khaddour.. Growth of sucrose crystals: determination of edge energy from the effect of added impurity on rate of step advance. Res. 36.. Porto Univ. A. Ferreira. [25] Albon. S.. I.. G. Bento. R. W. Growth of the faces of ammonium dihydrogen phosphate crystals in the presence of ionic species. 17 .. 355. (2). L. 2002.. 373-382. Rocha. N. 46.. N. Acta Cryst. Davey. Acta Crystallographica 1962. N. (3-4). Solvent entropy contribution to the free energy of protein crystallization. (8-10). Gast.. J. P.ebook777. [19] Kubota. A. Halcrow.. D58.. D. Journal of Crystal Growth 1974. I. Porto.ebook777. M. D. Experiments and kinetic-adsorption model. [26] Sgualdino. 480-488. 152. R. The kinetics of crystal growth in the presence of tailor-made additives. W. 212. N. Kinetics and thermodynamics of sucrose crystallization from pure solution at different initial supersaturations. Journal of Crystal Growth 2006. 1208-1214. S.. A.. [16] Kubota. Cryst. [24] Adamson. R. [18] Vekilov. 2011. Mullin. (1-3... N. L. 292. 23. 15..free ebooks ==> www. Petsev. Pastero.. J. Mullin. F. Sucrose crystal growth in the presence of dextran of different molecular weights. J. Journal of Crystal Growth 2000. N..25.. Bento. 203-208. I.. www. Journal of Crystal Growth 2012. (1). 474-476. Surface Science 2010. 1611-1616. G.. (1). (3).-T. Feeling-Taylor. W. Cincotti. Crystal Research and Technology 2001. 2011. [15] Black. [17] Khaddour. Journal of Crystal Growth 1995. A. [20] Kubota.. Tech. Vaccari. Journal of Crystal Growth 1986.. 765-774.. Wiley Interscience: New York 1997.. W. A. 79. Face- by-face growth of sucrose crystals from aqueous solutions in the presence of raffinose. J. Aquilano.. [23] Khaddour.. Dunning. G. M. 89-94.. I. Yau. M. A.. Yokota. 749-769. The combined influence of supersaturation and impurity concentration on crystal growth. J. Mullin. A. L. Crystallization of sucrose from pure solutions and in teh presence of dextran of different molecular weights. W. (13-14).. A.. A kinetic model for crystal growth from aqueous solution in the presence of impurity. (5). Effect of Impurities on the Growth Kinetics of Crystals.... P. 92-103.com .. M. F. F. 604. S. Rocha.com Modeling Effects of Impurities on Crystal Growth 91 [14] Davey. A. [21] Khaddour.

A. Journal of Crystal Growth 1998. The Physical Chemistry of Surface Films.free ebooks ==> www. G. P. 30 (1). 88. A. W. [34] Malkin. Simulation of 2D nucleation and crystal growth. [30] Hakins. 191. R. Khaddour [27] Khaddour. F. Porto University... J. Defect Structure of Macromolecular Crystals. Reinhold: New York. The Chemical Catalog Company: New York 1925. Meekes. B. Morphology of orthorhombic n-paraffin crystals: a comparison between theory and experiments.1016/0022-0248(75)90212-2. Roy. Chemical Engineering Department. [31] van Enckevort. Journal of Crystal Growth 1998. (3). [29] Hardy. Unpublished data. [36] Gilmer. [33] Valcic.. 2010. Journal of Crystal Growth 1975. Proc.. P. The influence of dislocations on the growth rate of saccharose crystals.com 92 Issam A.. van Enckevort. 117. [35] van Hoof. 124-137.ebook777. [28] Langmuir. 59-69. 129-136. J. Impurity blocking of crystal growth: a Monte Carlo study.. 2010. J. P. Transfer of impurities into crystals in industrial processes: mechanisms and kinetics. I. (2).. Kuznetsov. (4). G. J..... The Influence of Chemical Constitution upon Interfacial Tension. C.. Grimbergen. 183.. ed. H. (Doctoral Thesis). Y. McPherson. In Colloid Symposium Monograph. M. W. 303-313. . p 48. W. W. London 1913. Soc. A. [32] Vasanth Kumar. P. Faraday Symposia of the Chemical Society 1977.. 1952. D. Journal of Structural Biology 1996. I. H. 12.. A. J. Porto. K. C. DOI: 10. 861-872.. V. P. van den Berg. Bennema. 441-455.. F.

7. 59. 3. 42. 34. viii. 16 alters. ammonium. 73. 2. 81 candidates. 40. viii. 76. 80. 17. 25. 17. viii. 28. 2. 6 bending. 1 additives. 7 bonds. 75 configuration. 55. 72. 54. 91 adsorption. 47 base. 48. 53 atomic force. 20. 2. 6. 75. 57. viii. vii. 21 Boltzmann constant. 41. 11. 13 benefits. 59 bonding. 26. 5. 44 www. 25. 5. 30 B composition. 90. 82. 76.com INDEX borate crystals. 11 atmospheric pressure. viii. 1 actuators. 37. 60. viii. 30. 11 computer. 26 A borate melt structures.com . 54 Brazil. 55 AFM. 55 cleaning. 19. 6. 25. 27. 47. 31 boundary layer. 79. 13. 46 active site. 11 chemical(s). 53. 41. viii. 4. 39. vii. 89. 31 complexity. 30. 40. 17 compressibility. 11. 78.ebook777. 25. viii. 34. 9. 91 advancement. 56. 71. 56. 91 88. 90 breathing. 9. 58. 3 alkali niobates. 26. 71. 31 chemical reactions. 19 atoms.ebook777. C 90. 30. 3. absorption spectra. 76 bulk crystals. 9. 44. ix. 53. 46 compression. 9. 44. 36. 27. 66 carbides. 42. 47. 72 clusters. 2 cation. 47. 25. 3 aqueous solutions. 91 chemical stability. 36. 61. 89. 4. 83 constituents. 22 compounds. 15. ix. 53. 3. 4. 78. 13 acid. 39. 16 China.free ebooks ==> www. 66 commercial. vii. 79. 30. 31 attachment. vii. 72. 25. vii. 16. 60 74 academic motivation. 88 color. 89 amplitude.

47 diaphragm. 72. 89. 55 crystal structure. 73 64. 65. 7. 41. 17. 64. 6 fluid. 47 dielectric constant. entropy. 90. 53. F 31. 3 D evacuation. 72. 22. 32. 83 electron microscopy. vii. 40 decay. 20. 47. 9.ebook777. 44. 73. 32. 83. 11. 47. 84 . 61. 11 crystal growth systems. 89. 31 dissociation. 61. vii. 62. 9. 32. viii. ix. 20 DOI. 28 crystalline. 1 contradiction. 29. 19. 60. 72. 9. 82 diffusion. 64. 15. 58. 44 financial. 54. 63. 33. 7. energy transfer. 55. 72. 67. 79. viii. 88. 92 crystal growth. 20. 30. 28. 59. 1. 17 deposition. 55. 6 47 electromechanical coupling. 41. 88. 30 cracks. 5. 8. 91 crystals. 9.free ebooks ==> www. 9. 1 detection. 63. vii. 6 corrosion. 60. 63. 9. viii. 63. 31. 36. 11. 3. 67 40. 31 75. 17 evolution. 5. 28. 71. viii. 37. 55 films. 59. 17. 84. 55. 27 density functional theory (DFT). 61. 91 energy. 37. 13 electroluminescence. 54. 92 digital cameras. 57. 88 83. 84 coordination. 13 diversity. 88 filters. 47 electric field. 90 cost. 84. electron. 7. 37. 53. 13. 91. 76. 62. 66. 2. 54 crystal quality. 74.com 94 Index Constitution. 11. 65. 6. 56. 61. 27. 64. 73. 19 fatty acids. ix. 67 cooling. 55. 17. 90. 5. 11. 66. 26. 11 distribution. 90. 73 64. 60. 8 financial support. 55. 58. 66 excitation. viii. 72. 74. 67 crystallization. 74. 7. 58. 61 detachment. 3 defects. 65. 80. 2. 66. 83. 31 correlation. viii. 55. 36. 27 dislocation. doping. 26. 2. viii. 9. viii. 83. 88 dielectric permittivity. 3. 16. 57. equilibrium. 8. 91 62. 63. 53. 3. 20. 32. 26. 14 crystal surface. 61. vii. crystallization kinetics. viii. 40. 45. 53. vii electric charge. 28. 32. 88 displacement. 91. 30 decomposition. 3. 53. 21 etching. 18. 28. 73. 74. 54. 73. 2. 56. viii. 89. 59. 1. 92 equipment. 66 diffraction. 66 10. 83. 92 E crystal growth processes. 41. 6. 18. 11. 25. 19. 80 diodes. viii. 73 depth. 6. 30. 13. 25. 27. 59. 25. 60. 2. 47 fabrication. 73. 62. 2. 66. 22. 59. emission. 38. viii. 57 force. 16. 5. 63. 55. 42. 73. 67. 31 fluorescence. 65. 9. 75. 26. 56. 16. 9. 11. 66. 26. 65. 21. 72. 53. electrolyte. vii. 65. 53. 15. 26.

25.com Index 95 formation. 81 inhibition. 37. 80 Hamiltonian. 75. 71. 78. ix. 6 leakage. 71. 7. 19. ix. 71. 71. 79. 26. 37. 89 impurities. 92 kinks. 30 hydroxyl. 5. H 90. 54. 17. 2. 11 liquids. 7. 89. 58. 11. 38. 28. 83 lifetime. 71. 19. 18. 92 growth mechanism. 7. 21 lens. ix. 11 irradiation. 31 laser radiation. 74. 58. 2. 17. 63 hypothesis. 41. 1. K 79. 57. 75. 30. 54. vii. vii. 4. 82. 83. 15. 75 hydroxyl groups. 82. 89. 87. 36. 15 integration. 6. 4. 55. 90. 60 ideal. 79. 1. ix. 4 luminescence. 73. 40 lasing threshold. 78. 5. 89. 55. 90. 67. 58 host. 84. 53. 5. 81. 80. 33. 6. 53. 72. 81. 59 germanium. 60. 54 glucose. 26. 28. 4. lattice parameters. 13. 11 fructose. 2. 37. 5. 82 luminescent materials. 15. 54. 1. 60. 20 83. 55. 61. 28 growth rate. 83 lasers. 77. 30. 88 G interface. 61. 27. joints. 26. viii. 7. viii. 28 hydrogen. 19. 66 L hybrid. 18. 61 Hydrothermal crystal growth. 58. 7. industries. vii. 92 kinetic model. 47 glasses. 55. 80 inhomogeneity. 89. 86. 72. 27 isomerization. viii. 6. 5. 27. 38. 56. 76. 4. 55. 34.com . 36. 5. 72. J 32. 83. 38. 39. 32. 84. 83. 83 liquid phase. 77. 73. 91 kinetics. 55.ebook777. 15. 90 ions. 8 89. 4. viii. 60 hydrogen atoms. 91. 27. 1. viii. 29. 61 image(s). 76. 54. 3. 31 issues. 38. ix. 40. 73. 17. 83. 74. 60. viii. 59. 17 hydrothermal system. 47. 8. 91 industry. 84. 20. 5. 48 www. 87 growth. 72. 17 intermolecular interactions. 42. 58 hydrothermal process. 40. 35. 64 glass transition. 63 luminescent efficiencies. 29. 15. 58. 72. 39. 87. 78. 44. 22. 9. 18. 6. 83 light. 72.free ebooks ==> www. 57. 46 Germanium Oxide. 88. 80. 36. 32 I low temperatures. 28. 57 19 lattices. 9. 54. 25 Luo. 44. 26. 82. 74. 88 geometry. 40. 92 free energy. 22. 17. 88. vii. 72. 83. 84. vii. viii. 91. 21. France. 8. 3. 56.ebook777. 83. 40. 20. 74. 17 85. 31 height.

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96 Index

nickel, 17
M nitrides, 3
Nobel Prize, 28
macromolecules, 73, 83, 89
nuclear magnetic resonance, 28, 49
magnetic resonance, 28
nucleation, ix, 71, 78, 81, 82, 90, 91, 92
magnitude, 6, 7
nucleus, 75
management, 19
nutrient, 5, 7, 11, 18, 19, 20, 22
manufacturing, 11
mass, 5, 7, 26
materials, vii, viii, 1, 3, 4, 7, 11, 13, 15, 19, O
25, 26, 32, 54, 55
matrix, 15 oligomers, 54
matter, 72 optical properties, viii, 53
measurement, 35, 38, 39, 74 ordered layer structures, viii, 53, 57
media, 9 oscillators, 13
melt, viii, 2, 25, 26, 27, 28, 29, 30, 31, 32, overlap, 54, 55
34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, oxidation, 4
45, 46, 47, 74, 90 oxygen, viii, 9, 13, 26, 30, 34, 35, 38, 40,
melting, vii, 1, 16, 26, 35, 36, 40, 42, 44, 45 41, 42, 44, 45, 47
melting point(s), vii, 1, 16, 35, 40, 45
melts, viii, 25, 26, 27, 30, 31, 32, 35, 38, 40,
41, 44, 47 P
metal ion(s), 38
Mg2+, 36 parallel, 22, 41, 57, 89
microcavity, 54 partition, ix, 71, 74, 75, 90
microscope, 21 passivation, 8
microscopy, viii, 53, 55, 82 peptide, 73
microstructures, 4 perforation, 19
military, 13 permission, 87
models, viii, ix, 26, 71, 73, 80 petroleum, 53
modifications, 9 phase diagram, 9, 11, 15, 17
mole, 73, 77 phase transformation, 2
molecular mobility, 6 phase transitions, 2, 3, 4, 9, 22
molecular orientation, 81 phosphate, 6, 91
molecular structure, 55, 56 phosphates, 3
molecular weight, 73, 86, 91 photographs, 56, 60, 61
molecules, viii, 8, 53, 54, 55, 57, 58, 59, 60, photoluminescence, 63
61, 62, 65, 66, 74, 78, 80, 83, 88 physical properties, viii, 6, 25
monolayer, 57, 58 piezoelectric materials, vii, 1
morphology, 3, 4, 6, 36, 37, 72, 89 piezoelectric properties, 13, 15, 17, 22
piezoelectricity, 11, 22
PL spectrum, 64
N platinum, 30, 35, 37
polar, 6
nano-crystals, 55 polarity, 6
nanoparticles, 3 polymer(s), viii, 26, 42, 45, 54, 73

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Index 97

population, 40 scattering, 28, 29, 30
preparation, 4, 18, 20 scattering intensity, 29
probe, 21 science, 89
programming, 17 security, 17, 21
project, 83 sediments, 13
propagation, 61 seed, 5, 6, 7, 18, 19, 20
proportionality, 88 segregation, 74
protein crystallization, 91 semiconductor(s), 54
pure water, 9, 18, 20 semiconductor lasers, 54
purity, 9, 73, 74 sensitivity, 28
sensors, 13, 17
shape, ix, 43, 46, 56, 71, 72, 78, 89
Q signals, 29
signal-to-noise ratio, 29
quantum yields, 59
silica, 9
quartz, vii, 2, 3, 4, 8, 9, 10, 11, 12, 13, 15,
silicon, 9, 11, 18, 90
16, 17, 18, 19, 20, 22, 61
simulation, 40
single crystals, vii, 2, 3, 4, 5, 6, 8, 13, 17,
R 19, 22, 54
sintering, 4
radiation, 28, 29, 38 SiO2, v, vii, 1, 2, 8, 9, 10, 11, 12, 13, 14, 15,
radius, 75 16, 17, 18, 19, 20, 22
Raman spectra, viii, 26, 30, 31, 32, 34, 35, sodium, 3, 6, 15, 17
37, 38, 39, 40, 42, 43, 45, 46, 47 sodium hydroxide, 6
Raman spectroscopy, viii, 25, 28, 30, 40, software, 31, 40
41, 44, 47, 49 solid solutions, 15, 20
reasoning, 84 solid state, 54, 73
recrystallization, ix, 6, 15, 54, 71, 73 solubility, 3, 5, 6, 7, 9, 15, 18, 20, 73, 83, 84
red shift, 59 solution, viii, ix, 2, 3, 5, 7, 15, 19, 26, 37,
regression, 83, 85 39, 40, 47, 59, 71, 72, 73, 74, 76, 77, 80,
rejection, 74 83, 87, 90, 91
researchers, vii, 2 solvents, 3, 5, 8, 22, 90
resolution, 28, 29, 30 species, 6, 19, 20, 74, 75, 91
response, 31 specific adsorption, 88
retardation, 72, 76, 79, 83, 88 spectroscopic techniques, 29
rings, viii, 25, 32, 33, 35, 36, 37, 38, 39, 40, spectroscopy, 28, 32, 47, 66
41, 44, 47 spin, 55
room temperature, 6, 28, 32 stability, vii, 1, 9, 13, 17, 32
Russia, 13 state(s), 4, 9, 15, 60, 66
rutile, 15, 16, 18 steel, 7, 17, 30
stoichiometry, 11
stress, 20
S stretching, 41, 42, 44, 46
strong interaction, 5
saturation, 73 structural changes, 40
scaling, 40

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98 Index

structural defects, 11 transport, viii, 5, 6, 19, 20, 26, 28, 53, 55,
structural modifications, 90 66
structural transitions, 4
structure, vii, viii, 2, 10, 11, 13, 14, 15, 16,
17, 20, 26, 27, 28, 30, 32, 33, 34, 35, 36, U
40, 41, 42, 43, 44, 54, 55, 58, 59, 66, 72,
uniform, 9, 18
80, 90
universal gas constant, 73
substitution, 15, 17
substrate(s), 44, 61
succession, 55 V
sucrose, ix, 71, 73, 74, 75, 79, 81, 82, 83,
84, 85, 86, 87, 88, 89, 90, 91 vacuum, 55
supercooling, 6 valence, 15
suppression, 78 valve, 21
surface tension, 27 vapor, viii, 2, 53, 55, 59, 66
surfactant(s), 73, 84 variables, 78, 80
synthesis, 6 variations, 81
Syria, 71 velocity, 76, 79
vessels, 5, 7, 17
vibration, 39, 42, 44, 46
T
viscosity, 6, 26, 27
volatilization, vii, 2
techniques, vii, viii, 1, 2, 4, 5, 9, 25, 27, 28
technology, 4
temperature, vii, viii, 2, 3, 4, 5, 6, 7, 9, 11, W
13, 16, 17, 18, 20, 22, 25, 26, 27, 28, 29,
30, 32, 35, 37, 38, 40, 41, 44, 47, 49, 61, war, 4
73, 78, 81 Washington, 49
terraces, 80 water, 3, 6, 7, 15, 18, 20, 30, 84, 86
thermal decomposition, 4 wavelengths, 59, 61, 66, 67
thermal expansion, 7 weakness, 30
thermal stability, 2, 17, 54 workers, 31
thermal strain, vii, 1, 11 worldwide, vii, 2
thermodynamical parameters, 11
thermodynamics, 91
time control circuits, vii, 1 X
time resolution, 29
total energy, 31 X-ray diffraction(XRD), viii, 28, 53, 55, 57,
toxicity, vii, 2, 6 58, 66
transformation(s), 13, 16, 18, 26, 42, 47
transition temperature, 9, 15
Y
transmission, 28
transmission electron microscopy, 28 yield, 4, 62
transparency, 38, 41