03 Lin L

Chapter 1 General introduction
1.1 Introduction Colloidal semiconductor nanocrystals (quantum dots, QDs) have generated great fundamental and technical interest due to their novel size-dependent properties.1-4 This new class of nanomaterials has come under intensive investigation for their linear and nonlinear optical properties in connection to optoelectronic devices and biomedical tags.5-10 The most striking feature of nanomaterials is that their chemical and physical properties differ markedly from those of the corresponding bulk solids. This behavior can be ascribed to two basic reasons as follows: The first reason is the high surface to volume ratio (i.e., the number of atoms at the surfaces or grain boundaries of the crystalline regions is comparable to the number of those that are located in the crystalline lattice itself). Smaller nanoparticles have higher surface to volume ratio. The second one is that the de Broglie wavelength of electrons and/or holes becomes comparable to the crystallite size of the nano-sized semiconductors. Under such conditions, the charge carriers can be determined by the classical particle-in-a-box quantum model, where the band gap is inversely proportional to the dimensions of the nanocrystals. The band gap increases if semiconductor particles become smaller than the Bohr radius of the exciton, and a transition from a continuous distribution of energy levels to discrete energy levels is caused. In this regime, the clusters still possess short-range structures that essentially mimic the bulk semiconductors from which they are derived. Currently, the development of general techniques for the fabrication of high-quality nano-sized semiconductor has been a major goal of material chemists. The following
subsections will provide a review and highlight recent progress of these synthetic methods.
1.2 Synthetic methods The preparation of nearly monodisperse nanoparticles is essential to distinguish the truly novel properties inherent to the nano-structure from those associated with structural heterogeneity or polydispersity. Samples with standard deviations ca.5% in diameter are referred to as monodisperse in this thesis. Many synthetic methods for the preparation of monodispersed material have been reported, and the following subsection will review several of these approaches.
1.2.1 Arrested precipitation Perhaps the simplest method for preparing small particles is arrested precipitation from a solvent as a colloid. In turn, the simplest manifestation of this approach involves the solvent itself acting as the surface stabilizer of the small clusters, leading to so-called organosols. For example, stable colloids of TiO2 can be generated by the hydrolysis of TiCl4 or equivalent alkoxides in water with the surface hydroxyl groups on the TiO2 clusters acting as the colloid stabilizer.11, 12 In addition, the unique luminescent properties of TiO2 prepared by this route have been reported.13 Other types of metal oxide nanoparticles such as ZnO14 and SiO215 have also been prepared by similar techniques of hydrolysis of the corresponding metal salts or metal alkoxides in alcohol or aqueous solvents. The challenge of this method is to obtain a solid material that is dense, inorganic and amorphous from a room-temperature liquid (not a melt), which is generally
a homogeneous mixture of organic compounds. A similar approach has been explored to synthesize piezoelectric lead zirconate titanate (PZT)16 and ferroelectric barium titanate nanoparticles.17 As for the synthesis of metal chalcogenide nanoclusters, the addition of organic molecular capping agents is an easy technique to control the growth of nanoparticles. These agents, typically anionic, are added to a semiconductor precipitation reaction. They intercept the growing clusters and prevent further growth by covalently binding to the cluster surface. Thiolate are the most commonly used capping agent since SH has a high affinity with most of the metal ions. In most cases, the metal salt is mixed with the capping agent and then the chalcogenide source is introduced either by bubbling hydrogen chalcogenide or adding the corresponding solution of chalcogenide salt into the mixture. CdS, CdSe, CdTe, ZnS and Ag2S have been synthesized by using different types of thiols.18-24 Other capping agents, such as long chain arachidic acid, have been used to provide a suitable organic matrix for the epitaxial growth of CdS nanoparticles.25
1.2.2 Microemulsion Microemulsion is thermodynamically stable, isotropic dispersion of oil and water with a thin film of surfactant molecules adsorbed at the water and oil interface. By varying the composition of suitable components and the HLB (hydrophilic-lipophilic balance) value of the surfactants, one can obtain oil-swollen micelles dispersed in water (known as oil-in-water microemulsion), or water-swollen micelles dispersed in oil (known as water-in-oil microemulsion). The latter is also called an inverse microemulsion. Due to the small dispersion sizes, usually 5 to 20 nm in diameter, 3
microemulsions are transparent or translucent. In contrast to the colloidal approach, the micellar reagent acts as a physical boundary rather than a true surface capping agent. Normal vesicles using dihexadecyl phosphate, cetyltrimethylammonium chloride (CTAB) or dioctadecyldimethylammonium chloride (DODAC) can be produced in water with diameters of the order of 150 to 300 nm. Dissolution of metal ions in these vesicles followed by a precipitation with H2S or Sodium Sulfide can lead to semiconductors of up to 5 nm inside the micelles.26 Reverse micelles using bis(2-ethylhexyl) sulfosuccinate salts (AOT) allow for the formation of small water pools (< 10 nm and the size of water pools is dependent on the water/AOT ratio) in nonpolar solvents, such as hexane, cyclohexane or 2,2,4,trimethyloctane. Then the metal ions can be encapsulated into the pools followed by the chalcogenide treatment. This process can generate semiconductor nanoparticles with a relatively monodisperse distribution. In most cases, the pools formed by this technique result in spherical nanoparticles. However, it is found that the shape of the pools can be controlled by incorporating some other additives, which can produce different shapes of nanoparticles.27 CdSe and ZnSe nanorod,28 triangular CdS nanoparticles29 have been reported by using this method. In addition, many ultrafine powders of metal oxides such as ZnO, PbO, CdO, perovskite-type mixed oxides and magnetic cobalt ferrite can also be derived from such methods. Nonionic surfactants are also excellent templates to synthesize semiconductor nanoparticles. With Igepal CO 520 as the surfactant, monodisperse silica-CdS nanocomposite spheres can be prepared and then etched with strong acid. The etched silica particles have geometrically tailorable voids and can be used in catalyst support media.30-31 Stupp first reported the growth of stable CdS-organic superlattice obtained by
a liquid-crystalline phase formed from nonionic amphiphiles oligoethylenexoide oleyl ether.32 The hydrophilic parts can conjugate with the cadmium ions, while the hydrophobic group can self-assemble into a hexagonal mesophase, which plays the major role in the formation of the superlattice morphology.
1.2.3 Passivation in polymer matrix As compared to inorganic materials, polymers have the advantages of superior mechanical properties and excellent film processability. Nanocomposites consisting of inorganic nanoparticles and organic polymers exhibit a host of mechanical, electrical, optical and magnetic properties, which are far superior as compared with those of the individual components.33 These desirable properties are derived from a complex interplay between the building blocks and the interfaces separating the building blocks. Two main approaches have been used to produce these nanocomposites. The first approach is an in situ precipitation method. In a typical experiment, the matrix material and metal ions are mixed in solution and then exposed to the counterion (S2-, Se2-) in the form of gas or as ions dissolved in solution. The composite can be cast as a film before or after exposure to the counterion.33 Take the PbS nanoparticles for example, if poly(vinyl pyrrolidone) (PVP) is the matrix material for PbS nanoparticles, a solution of PVP and Pb2+ can be prepared in water. This solution can then be exposed to H2S gas in order to form the PbS and cast as a film. In this particular reaction, the crystalline semiconductor forms extremely quickly and yields a wine-red solution. An alternative in situ polymerization method is also developed; a well-defined nano-sized semiconductor is first prepared using the monomer as a capping agent, then the nanoparticles undergo 5
the homopolymerization or copolymerization process with other monomers to get polymer nanocomposites.34 The second one is an ex situ method. In this method, semiconductor clusters are first prepared by using capping agents as the stabilizers, and then the nanoparticles are dissolved in a solvent along with a soluble polymer. This mixed solution can be cast to produce a polymer film doped with the semiconductor cluster. This simple approach provides some new examples of interesting photoconductive or photovoltaic nanocomposites. For instance, CdS/PVK35 and CuS, ZnS, CdS in polyacrylonitrile36 have been reported.
1.2.4 Encapsulation in the dendrimer template Dendrimers are a new class of three-dimensional, man-made macromolecules produced by an unusual synthetic route, which incorporates branching groups to create a unique novel architecture.37 Exceptional features of the dendritic architecture, include a high degree of structural symmetry, a density gradient displaying an intra-molecular minimum value and a well-defined number of terminal groups, which are chemically different from the interior. The combination of these features creates an environment within the dendrimer molecule that facilitates the trapping of guest species. Recently, dendritic polymers have been used as soluble templates/unimolecular reactors from which nano-clusters of inorganic compounds or elements can be synthesized. The basic concept involves using dendrimers as hosts to pre-organize small molecules or metal ions, followed by simple in situ reaction, which will immobilize and stabilize domains of atomic or molecular guest components (inorganic compounds as well as elemental 6
metals). Additionally, the dendrimer peripheral groups can be used to control the solubility. CdS/dendrimer nanocomposites are first reported by using PAMAM as the stabilizing host. The synthetic conditions, such as the dendrimer type, solvent, pH value can affect the optical properties of CdS nanoparticles.38 In addition, carboxy-terminated PAMAM dendrimers have been utilized for the synthesis and stabilization of ferrimagnetic iron oxide nanoparticles dendrimer.39 In the above mentioned efforts to prepare dendrimer nanocomposites, primarily interdendrimer composites are obtained; such materials have been shown to be agglomerates in which multiple dendrimers stabilize relatively large CdS nanoparticles. Intradendrimer CdS nanocomposites have been synthesized, and they are sequestered in individual dendrimers, which can prevent the nanoparticles from aggregations. Meanwhile, different sizes of CdS nanoparticles are prepared by changing the generation of the dendrimers.40 The approaches described here for preparing dendrimer-encapsulated nanoparticles take advantage of each of the unique aspects of the dendrimer structure: the chemistry of the terminal groups, the generation-dependent size, the three-dimensional structure, the low-density core and endoreceptors present within the dendrimer interior. Due to the dramatic developments in the design and characterization of dendrimers themselves, nanocomposite of dendrimers will attract increasing attention for their potential applications in biosensor, catalyst, self-assembly, engineering etc.
1.2.5 Organometallic method A powerful method for the preparation of semiconductor nanocrystallites has been described by Bawendi et al.41 Solutions of dimethylcadmium ((CH3)2Cd) and tri-noctylphosphine selenide (TOPSe) are injected under Ar atmosphere into hot tri-noctylphosphine oxide (TOPO) in the temperature range 120-300 C. This results in TOPO capped nanocrystallites of CdSe. The combination of tri-n-octylphosphine and trin-octylphosphine oxide (TOP/TOPO) allows for slow and steady growth conditions above 280C. This method has advantages over other synthetic methods; including the near monodispersity and the fact that gram scale amount of material can be produced. In addition, the nano-sized semiconductors obtained by this method have high luminescence quantum yields and narrow luminescence width. CdS, CdSe, CdTe,41 CdSe/CdS42 and CdSe/ZnS43 chalcogenide nanoparticles have been synthesized and well studied. Recently, transition oxide nanoparticles have been prepared by a nonhydrolytic solution based reaction at elevated temperatures.44 In addition to using TOPO as the coordinating solvent, carboxylic acid45 has also been utilized to prepare high-quality and highluminescent III-V semiconductor nanocrystals. In addition, the shape of the colloidal semiconductor nanocrystals can be tuned by the growth of nanoparticles in a mixture of aliphatic phosphonic acid and TOPO. Nanorods, arrow-, teardrop-, tetrapod- and branched tetrapod-shaped CdSe nanocrystals have been achieved.46, 47 The major limitation of this organometallic method is the use of hazardous compounds such as dimethylcadmium especially at high temperatures. One approach to overcome this problem is to use more environmental friendly chemicals, such as cadmium oxide,48 cadmium carbonate, cadmium stearate and cadmium acetate.49
It is found that high-quality nanocrystals can be produced from alternative route. For example, Yu et al.50 produced high-quality CdS and other II-VI semiconductor nanocrystals in noncoordinating solvents such as octadecene (ODE). The introduction of noncoordinating solvents further enhances the possibility of implementing greenchemical principles into the design of synthetic schemes for colloidal nanocrystals.
1.2.6 Single molecular precursor thermolysis method Another approach for overcoming the above problems involves the use of the single molecule precursor, a single compound containing all elements required within the nanocrystallite, such as alkyldiseleno- or alkyldithio-carbamate complexes.51,
52
The
fabrication of semiconductor nanocrystallites from single molecule precursors is a one step process, typically carries out at temperatures in the range of 200-250 C, using tri-noctylphosphine oxide (TOPO) as the coordinating solvent. CdS,51, 53 CdSe,51, 53 ZnS53 and CuSe54 nanoparticles have been prepared by using the dithio- and diseleno-carbamate complexes. A similar approach in which non-airsensitive lead(II) alkyldithiocarbamates55 are thermally decomposed under controlled conditions, leads to the synthesis of cubic phase PbS nanocrystallites. Self-capped CdS nanoparticles have also been synthesized by heating a novel cadmium dithiocarbamate complex,
Cd(S2CNMe(C18H37))2, at high temperature in a nitrogen atmosphere.56 Cheon et al. utilized long alkyl amines instead of TOPO as the capping agent to prepare the II-VI ZnSe and ZnTe nanocrystals.57, 58 The single-molecular precursor is an air-stable [Zn(SePh)2][TMEDA] or [Zn(TePh)2][TMEDA] complex, which effectively produces different sizes of ZnSe or ZnTe QDs depending on the growth temperatures. 9
The shape of the nanocrystals can be tuned by varying the composition of the capping surfactants. In addition, they provide a novel method to control the CdS nanorod architecture by using a monosurfactant hexadecylamine (HDA) system.59 Different shapes of CdS nanocrystals can be obtained by simple adjustment of the reaction temperature or the precursor concentration. It is found that different phases of nanoparticles can be obtained at different temperature stages, which can control the formation of the nanocrystals. Capping agents with bifunctional groups such as ethylendiamine are also used to prepare CdS nanowires with quantum confined diameters and lengths from 150 nm to 250 nm from a cluster precursor Cd2(S2Et2)4.53 Nucleophilic attacked by the diamine groups at the thione can remove the capping groups.60 Alivisatos first reported a new nonhydrolytic single precursor approach to synthesize transition metal oxide nanocrystals by thermolysis of metal cuperferron complexes.61 Compared with those transition metal oxides nanoparticles synthesized from the traditional wet colloid method, metal oxide nanoparticles prepared by this method have no hydroxyl groups and less surface defects, which have significant applications in catalysis, magnetic data storage and so on. In addition, nano-sized Cd3P2 semiconductors have been prepared by using a novel single source precursor.62
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1.3 Potential applications 1.3.1 Optoelectronics devices The large surface area of a nanocrystal and the surrounding medium, such as the capping agent, can have a profound effect on the properties of the particle. Defects within the particle act as electron/hole traps which lead to nonlinear optical effects. For example, the size-dependence of the third-order nonlinear absorption of CdS nanocrystals is studied by using nanosecond Z-scan method.63 Polymer CdS nanocomposite has been prepared and the nonlinear optical properties have been studied. It is found that the nonlinear absorption is greatly enhanced as the particle size decreases, which is predicted by the quantum size effect.64 A design for a solid-state laser, based on the luminescence properties of metal chalcogenide quantum dots (CdSe, CdTe, ZnSe, ZnTe), in a host material such as poly(methyl methacrylate) has been described.65 The wavelength of the emitted light is determined by the size of the nanocrystallites chosen. Bulk ZnS is an important inorganic material for light emitting applications. ZnS doped with various transition metal ions such as manganese is an efficient light emitting material. If such dopants are inserted in the nano-sized ZnS matrix, they can exhibit interesting magnetic and optical properties. The photophysical properties of ZnS:Mn66 and ZnS:Cu67 have been reported. These works suggest that the fabrication of the luminescent ZnS devices, with distinct optical properties, can be achieved by using ZnS nanocrystallites possessing spatially localized metal ions. Solar cells based on large band gap semiconductors usually TiO2 sensitized to visible light with dyes have recently emerged as promising inexpensive alternatives to conventional photovoltaic solar cells.68 The semiconductor is deposited onto a transparent 11
conductive oxide (TCO) electrode, through which the cell is illuminated. The TiO2 pores are filled with a redox electrolyte (I-/I3-) that acts as a conductor and electrically connects to a platinum electrode. Upon absorption of light, the dye adsorbed on the surface of the semiconductor injects an electron into the conduction band. The oxidized dye molecule is then regenerated by accepting an electron from a reducing agent present in solution. The cell open-circuit photovoltage is limited to the difference between the quasi-Fermi level for electrons in the semiconductor and the redox potential in the electrolyte solution. Such systems can reach solar to electric conversion efficiencies of about 10%, but are still not produced on a large scale mainly because of technical problems such as sealing. In 1994, a paper first reported the development of light-emitting diodes using a hybrid organic/inorganic electroluminescent device.69 The light emission originates from the recombination of holes injected into a layer of semiconducting p-paraphenylene vinylene (PPV) with electrons injected into a multilayer film of the CdS nanocrystals. The close matching of the energy level of the emitting layer of nanocrystals with the work function of the metal contact can lead to an operating voltage of only 4V while the operating voltage for PPV alone is 7V. At low voltages, the emission from the CdSe layer occurs. The color of this emission varies from red to yellow due to the size of the nanocrystals. At higher voltages the green emission from the polymer layer predominates. A bilayer light-emitting diod made with organically capped CdSe/CdS core/shell nanocrystals and PPV has been characterized by the same group subsequently. The epitaxial growth of the shell on the surface of CdSe can improve the quantum yields, the photo-oxidative stability and the electronic accessibility. These devices show significant
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improvements in quantum efficiency and lifetime as compared with the first CdSe device.70 1.3.2 Biological labeling There has been some exciting work in which biological molecules are attached or adsorbed to inorganic nanoparticles. Two different groups have simultaneously reported the use of CdSe nanoparticles with high photoluminescence as fluorescent dyes for biological molecules.71,
72
In both cases, highly luminescent CdSe nanocrystals are
surface-passivated with a thin layer of a larger bandgap material and then a conjugatable group is attached to the outer surface. One key in the synthesis is the production of watersoluble nanoparticles. Subsequently, the biological molecules are attached to the surface of nanoparticles and the localization of the molecules can then be imaged. The color of the fluorescent dye is a function of the nanoparticle size; thus different colors of dyes can be attached to a receptor of interest just by tuning the size of the nanoparticles. Adapting the complementary base pairing as the means to organize the nanoparticles, it is now possible for researchers to develop new diagnostic techniques in DNA quantitation and detection of diseases. For these biological applications, the alloyed quantum dots also can be made watersoluble and biocompatible by using a similar surface-modification and cross-linking procedures as reported for those binary quantum dots. If solubilized with mercaptoacetic acid and coated with a biopolymer or a synthetic polymer, the ternary dots are found to exhibit excellent optical properties such as a narrow spectral width, excellent photostability and high quantum yields, compared with those of high-quality binary nanocrystals reported before.
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1.3.3 Catalysis The large surface-to-volume ratio, along with the ability to tune the band gap, by varying the particle size, indicate that monodisperse semiconductors can be used as sensitizers and catalysts in photochemical reactions. The redox levels of the conduction and valence bands are especially sensitive to size quantization effects. Charge carriers generated after the light absorption migrate to the surface of the particles where they can reduce or oxidize surface-bound chemical species. One of the most studied oxidation reactions on semiconductor particles is the photoinduced dehydrogeneration of alcohol to aldehydes or ketones.73, 74 Photogeneration of hydrogen is carried out by irradiating the micellar solution containing ZnS, CdS and the co-precipitated nanoparticles.75 Currently, other catalytic applications of nano-sized semiconductor in condensation, isomerization, substitution and polymerization are also under intensive investigation. Although a wide range of synthetic methods is available for producing semiconductor nanocrystals, it seems that there is still a major problem associated with the reproducible preparation of robust materials of the kind that would be needed for technological applications. All of the above-mentioned methods have their own advantages. Colloidal method uses lower temperature and is easier to be manipulated, but it has problems with instability and more surface defects. Microemulsion methods can produce moderately monodisperse nanoparticles, but the product yield is very low. The interplay between polymer chemistry and quantum dots synthesis will undoubtedly become more important in the future. However, it is still a challenge to get monodisperse nanocomposites in a polymer matrix. The organometallic approach can produce welldefined nanocrystals with few defects and a high monodispersity of the size distribution.
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One of the drawbacks of this method is the use of toxic and volatile compounds during the experimental process. The use of single molecular precursor is a powerful method for the synthesis, shape control and engineering of nano-sized semiconductors with superior optoelectronic and physiochemical properties. The development and knowledge of this field are still limited now. In addition, in all of the reports on preparing nanoparticles from single source precursor method, high temperatures and the rapid injection are two indispensable conditions for the experiment. However, few studies report the synthesis of nanoparticles from single source precursor at moderate conditions, even at room temperature, which are much more desirable for future industrial applications.
1.4 Objectives of the project Our project mainly focuses on the synthesis, characterization and formation mechanism of several different types of semiconductor nanocrystals at elevated temperatures. The main objectives in this thesis are listed as follows: 1.4.1 Synthesis of semiconducting metal sulfide nanocrystals of CdS, ZnS and ZnxCd1-xS with various sizes and shapes by the thermal reaction of metal salts and sulfur in long-chain amine In this part, a green chemical route to high-quality CdS, ZnS and ZnxCd1-xS nanocrystals is reported. It is a one-pot method using stable, commonly available precursors (metal salts such as metal stearate, acetate, chloride, and sulfate etc. as the cadmium source and elemental sulfur as the sulfide source). The coordinating solvents
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used in this study include a series of convenient high-boiling long-chain amines such as hexadecylamine, oleylamine, etc. Our research focuses mainly on the formation of cubic zinc-blende CdS and ZnxCd1-xS nanocrystals at elevated temperature in this synthetic approach, where rapid nucleation and instant termination of the crystal growth process are observed. This nucleation and growth feature makes the reproducible and controllable synthesis of nanocrystals with specific emission wavelength feasible. For the synthesis of CdS, ZnS and ZnxCd1-xS nanocrystals, the metal salt is dissolved in amine to form a metal-amine complex at an appropriate high temperature. To the resulting solution, elemental sulfur dissolved in amine is swiftly injected. The reaction mixture is heated at a certain temperature for some period of time to generate the desired metal sulfide nanocrystals.
1.4.2 Synthesis of CdS, ZnS and ZnxCd1-xS composites using bis(diethyldithiocarbamate)-cadmium(II)/zinc(II) compounds as single-source precursors CdS, ZnS and ZnxCd1-xS alloyed nanocrystals are obtained by the thermolysis method. The nanocrystal composition is expected to remain constant during the whole reaction process, yielding a homogeneous alloy that is uniform from the particle core to the surface. The alloyed nanocrystals will give a blue shift in the emission and absorption edge as compared to the binary CdS nanocrystals. The observed continuous shift of the absorption and PL spectra of the obtained nanocrystals with different compositions is the most direct evidence for the alloying process.
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(35) Dabbousi, B. O.; Bawendi, M.; Onitsuka, O.; Rubner, M. F. Appl. Phys. Lett. 1995, 66, 1316. (36) Yamamoto, T.; Kubota, E.; Taniguchi, A.; Dev. S.; Tanaka, K.; Osakada, K.; Sumita, M. Chem. Mater. 1992, 4, 570. (37) Zimmerman, S. C.; Lawless, L. J. Top. Curr. Chem. 2001, 217, 95. (38) Sooklal, K.; Hanus, L. H.; Ploehn, H. J.; Murray, C. J. Adv. Mater. 1998, 10, 1083. (39) Strable, E.; Bulte, J. W.; Moskowitz, B.; Vivekanandan, K.; Allen, M.; Douglas, T. Chem. Mater. 2001, 13, 2201. (40) Lemon, B. I.; Crooks, R. M. J. Am. Chem. Soc. 2000, 122, 12886. (41) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 1993, 115, 8706. (42) Peng, X. G.; Schlamp, M. C.; Kadavanich, A. V.; Alivisatos, A. P. J. Am. Chem. Soc. 1997, 119, 7019. (43) Hines, M. A.; Guyot-Sionnest, P. J. Phys. Chem. 1996, 100, 468. (44) Trentler, T. J.; Denler, T. E.; Bertone, J. F.; Agrawal, A.; Colvin, V.L. J. Am. Chem. Soc. 1999, 121, 1613. (45) Battaglia, D.; Peng, X. G. Nano Lett. 2002, 2, 1027. (46) Manna, L.; Scher, E. C.; Alivisatos, A. P. J. Am. Chem. Soc. 2000, 122, 12700. (47) Peng, X. G.; Manna, L.; Yang, W. D.; Wickham, J.; Scher, E.; Kadavanich, A.; Alivisatos, A. P. Nature 2000, 404, 59. (48) Peng, Z. A.; Peng, X. G. J. Am. Chem. Soc. 2001, 123, 183. (49) Qu, L. H.; Peng, Z. A.; Peng, X. G. Nano Lett. 2001, 1, 333. (50) Yu, M. W.; Peng, X. G. Angew. Chem. Int. Ed. 2002, 41, 2368. (51) Trindade, T.; OBrien, P.; Zhang, X. Chem. Mater. 1997, 9, 523.
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(52) Malik, M. A.; Revaprasadu, N.; OBrien, P. Chem. Mater. 2001, 13, 913. (53) Ludolph, B.; Malik, M. A.; OBrien, P.; Revaprasadu, N. Chem. Commun. 1998, 1849. (54) Malik, M. A.; OBrien, P.; Revaprasadu, N. Adv. Mater. 1999, 11, 1441. (55) Trindade, T.; OBrien, P.; Zhang, X.; Motevalli, M. J. Mater. Chem. 1997, 7, 1011. (56) Lazell, M.; OBrien, P. Chem. Commun. 1999, 2041. (57) Jun, Y. W.; Koo, J. E.; Cheon, J. Chem. Commun. 2000, 1243. (58) Jun, Y. W.; Choi, C. S.; Cheon, J. Chem. Commun. 2001, 101. (59) Jun, Y. W.; Lee, S. M.; Kang, N. J.; Cheon, J. J. Am. Chem. Soc. 2001, 123, 5150. (60) Yan, P.; Xie, Y.; Qian, Y. T.; Liu, X. M. Chem. Commun. 1999, 1293. (61) Rockenberger, J.; Scher, E. C.; Alivisatos, A. P. J. Am. Chem. Soc. 1999, 121, 11595. (62) Green, M.; OBrien, P. Adv. Mater. 1998, 10, 527. (63) He, J.; Ji, W.; Ma, G. H.; Tang, S. H.; Elim, H. I.; Sun, W. X.; Zhang, Z. H.; Chin, W. S. J. Appl. Phys. 2004, 95, 6381. (64) Du, H.; Xu, G. Q.; Chin, W. S.; Huang, L.; Ji, W. Chem. Mater. 2002, 14, 4473. (65) Sooklal, K.; Cullum, B. S.; Angel, S. M.; Murphy, C. J. J. Phys. Chem. 1996, 100, 4551. (66) Klein, J. D.; Herrick, R. D.; Palmer, D.; Sailor, M. J.; Brumlik, C. J.; Martin, C. R. Chem. Mater. 1993, 5, 902. (67) Huang, J. M.; Yang, Y.; Xue, S. H.; Yang, B.; Liu, S. Y.; Shen, J. C. Appl. Phys. Lett. 1997, 70, 2335. (68) ORegan, B.; Graetzel, M. Nature 1991, 353, 737.
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(69) Colvin, V. L.; Schlamp, M. C.; Alivisatos, A. P. Nature 1994, 370, 354. (70) Schlamp, M. C.; Peng, X. G.; Alivisatos, A. P. J. Appl. Phys. 1997, 82, 5837. (71) Chan, W. C. W.; Nie, S. M. Science 1998, 281, 2016. (72) Bruchez, M.; Moronne, M.; Gin, P.; Weiss, S.; Alivosatos, A. P. Science 1998, 281, 2013. (73) Fox, M. A.; Abdel-Wahab. A. A. J. Catal. 1990, 126, 693. (74) Kawai, M.; Kawai, T.; Naito, S.; Tamaru, K. Chem. Phys. Lett. 1984, 110, 58. (75) Hirai, T.; Shiojiri, S.; Komasawa, I. J. Chem. Eng. Jpn. 1994, 27, 590.
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Chapter 2 Experimental section
2.1 Chemical reagents Cadmium acetate (98%), cadmium sulfate (99%), cadmium chloride (99.99%), zinc stearate (90%), 1-hexadecylamine (90%), dodecylamine (98%), sulfur powder (99.98%), zinc oxide (99%), cadmium oxide (99.99%), cadmium hydroxide (98%), diethylamine (99.5%) and carbon disulfide (99.9%) were purchased from Aldrich. Cadmium stearate (90%) was purchased from Sterm Chemicals. Methanol (AR), toluene (AR and HPLC), chloroform (HPLC) and acetone (AR and HPLC) were purchased from Merck.
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2.2 General synthetic methods 2.2.1 Synthesis of CdS nanocrystals by the thermal reaction of metal salts and sulfur in long-chain amine
Cd(ST)2 was dissolved in hexadecylamine The mixture was heated to 295 oC under argon flow
Sulfur in dodecylamine was swiftly injected into this solution
The reaction mixture was then kept at 280 oC for the growth/annealing of the nanocrystals
A mixed solvent of methanol and acetone was used to precipitate the resulting nanocrystals from the solution, which were then isolated by centrifugation and decantation
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2.2.2 Synthesis of ZnS nanocrystals by the thermal reaction of metal salts and sulfur in long-chain amine
Zn(ST)2 was dissolved in hexadecylamine The mixture was heated to 288 oC under argon flow
Sulfur in dodecylamine was swiftly injected into this solution
The reaction mixture was then kept at 280 oC for the growth/annealing of the nanocrystals
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2.2.3 Synthesis of ZnxCd1-xS nanocrystals by the thermal reaction of metal salts and sulfur in long-chain amine
Cd(ST)2 and Zn(ST)2 were mixed and dissolved in hexadecylamine The mixture was heated to 270 oC under argon flow
Sulfur in dodecylamine was swiftly injected into this solution and the injected amount of sulfur was equal to the total molar amount of Zn and Cd precursors. The reaction mixture was then kept at 260 oC for the growth/annealing of the nanocrystals
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2.2.4 Synthesis of CdS nanocrystals using bis(diethyldithiocarbamate)-cadmium(II) compounds as single-source precursor
Cd(S2CNEt2)2 was fully dissolved in tri-n-octylphosphine
This solution was then injected into a hot (300 C) solution of tri-n-octylphosphine oxide and hexadecylamine The reaction mixture was then kept at this temperature for 30 minutes to produce CdS nanocrystals A mixed solvent of methanol and acetone was used to precipitate the resulting nanocrystals from the solution, which were then isolated by centrifugation and decantation
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2.2.5 Synthesis of ZnS nanocrystals using bis(diethyldithiocarbamate)-zinc(II) compounds as single-source precursor
Zn(S2CNEt2)2 was fully dissolved in tri-n-octylphosphine
This solution was then injected into a hot (300 C) solution of tri-n-octylphosphine oxide and hexadecylamine The reaction mixture was then kept at this temperature for 30 minutes to produce ZnS nanocrystals A mixed solvent of methanol and acetone was used to precipitate the resulting nanocrystals from the solution, which were then isolated by centrifugation and decantation
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2.2.6 Synthesis of ZnxCd1-xS nanocrystals using bis(diethyldithiocarbamate)cadmium(II)/zinc(II) compounds as single-source precursors
Cd(S2CNEt2)2 and Zn(S2CNEt2)2 were both dissolved in tri-n-octylphosphine
This solution was then injected into a hot (300 C) solution of tri-n-octylphosphine oxide and hexadecylamine The reaction mixture was then kept at this temperature for 30 minutes to produce ZnxCd1-xS nanocrystals A mixed solvent of methanol and acetone was used to precipitate the resulting nanocrystals from the solution, which were then isolated by centrifugation and decantation
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2.3 General characterization methods 2.3.1 Spectroscopic techniques (1) Photoluminescence spectroscopy Shimadzu RF-5301 PC spectrometer (2) Ultraviolet spectroscopy Shimadzu UV-1601 spectrophotometer (3) X-ray powder diffraction Siemens D5005 X-ray powder diffractometer operate at 40 kV and 40 mA (4) Inductively coupled plasma spectroscopy Thermal Jarrell As Duo Iris Inductively coupled-optical emission spectrometer
2.3.2 Microscopic techniques (1) Transmission electron microscopy JEOL JEM3010 transmission microscope (operate at an accelerating voltage of 300 kV)
2.4 Principles of characterization methods 2.4.1 Principles of photoluminescence spectroscopy (PL) Upon excitation, an electron will excite from valence band to conduction band, and a hole will form in the valence band accordingly, thus electron-hole pairs are created. The electron can subsequently recombine with the hole, either radiatively or nonradiatively. Radiative recombination can give rise to a relatively sharp emission band centered at approximately the band gap energy (exciton recombination band) and/or a relatively broad emission band centered at lower energies when deep traps are involved in the recombination process. For semiconductor nanoparticles, there is an increase in the band edge energy with decreasing particle size due to the quantum size effect. Therefore,
29
different emissions wavelength can be obtained by changing the particles size. This photoluminescence is very sensitive to the presence of absorbates at the nanoparticles surface. If the surface is well passivated, the photoluminescence wavelength maximum will be close to the absorbance edge with a little red-shift due to stokes shift. More surface traps will cause red-shift luminescence or even surface defects emission, and low quantum yield. In addition, the surface ion can also affect the luminescent properties of nanomaterials. In the case of nanocrystalline CdS particles, sulfur-rich and cadmium rich nanoparticles are prepared respectively and optical properties are studied. It is found that the sulfur can quench the luminescence while cadmium can improve the luminescence efficiency.
e-
CB
electron traps
excitation
photoluminescence
hole traps
VB
Figure 2.1 Schematic generation of photoluminescence emission of semiconductor upon excitation. CB: conduction band, VB: valence band, hole (h+) and electron (e-).
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2.4.2 Principles of ultraviolet and visible spectroscopy (UV-vis) The wavelengths of UV-vis radiation range from 800 nm to 200 nm and they are involved in excitation of valence electrons that commonly known as electronic excitation. Electronic excitation refers to moving electrons in ground state (lowest energy state) to excited state (higher energy state). The energy involved in the excitation is expressed as E1 Eo = h where E1 is the excited state and Eo is the ground state. There are basically three types of electrons in organic compounds that are important to UV-vis.1 The first type of electrons is found in saturated bond ( bond) and the amount of energy need to excite electrons in
bond exceeds what the UV photons possess. Hence, this type of electrons is not useful
in UV-vis. The second type of electrons is found in unsaturated bond ( bond). Electrons in bond can be easily excited and absorbed in the UV. The last type of electrons is electrons that are not found in any bond (n electrons). Like electrons, n electrons can also be excited by UV radiation and most compounds that contain n electrons absorb UV radiation. On extrapolating to molecules, UV-vis involves the excitation of electron from a bonding orbital to an anti-bonding orbital. Hence, electrons in bond are excited to antibonding orbital. Electrons in bonds are excited to antibonding orbital and n electrons are excited to either antibonding orbital or antibonding orbital. In this study that involves metal nanoparticles, UV-vis spectroscopy involves more than just simple transition from bonding orbital to antibonding orbital. It is produced by a collective excitation of electrons in the particles. This absorption band is often known as surface plasmon band.1 Basically, a dipole excitation across the particle sphere is
31
produced when the electrons move under the influence of electric field vector of the incoming light. This results in the production of the positive polarization charge that acts as a restoring force and makes the electrons to oscillate. Only the electron density on the surface of the particles can oscillate whereas the electron density in the interior of the particles remains constant. UV-vis has many applications in providing the electronic structure for aromatic and transition metal compounds.1 Compared to other characterization methods, the operation is fairly easy, sensitive and inexpensive. Quartz or glass can be used as the window material over the entire range thus allowing greater flexibility. On the other hand, surface plasmon band allows one to calculate the size of the particles. Nonetheless, most of the UV-vis absorption bands are generally broad and featureless.1 This would have limited its capability in the determination of the molecular structures. Although UV-vis is capable to determine the plasmon band for some transition metals, there are some important metal compounds notably surface-protected copper nanoparticles2 that have no feature in UVvis at all.
2.4.3 Principles of x-ray powder diffraction (XRD) XRD is used to obtain information about the structure, composition as well as state of polycrystalline materials.3 A few typical applications include identification of unknown based on the crystalline peaks, variable temperature studies, precise measurement of lattice constants and residual strains as well as refinement of atomic coordinates.3
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In order to understand how the interaction of X-ray with crystals yields a diffraction pattern and ultimately (in most cases) a three-dimensional crystal structure, it is necessary to know the basic diffraction physics. Imagine the ions or molecules are arranged in welldefined position to make up the crystal as shown in Figure 2.2. We can clearly observe that the ions form planes in three dimensions. Hence, when a monochromatic x-ray beam falls on the crystal, the beam will be reflected by each of the crystal plane. Each reflected beam will interact with each other and if they are not in phase, they will destroy each other and no beam will emerge. Conversely, when they are in phase, reinforced beams will emerge to produce a diffraction pattern.
Figure 2.2 Crystal structure of sodium chloride: (+) Na ions and (-) Cl ions. The mathematical expression for this kind of interaction is given by Braggs law: n = 2dsin where n is an integer, is the wavelength of the radiation, d is the perpendicular spacing between adjacent planes in the crystal lattice and is the angle of incident and reflection of the X-ray beam. This equation states that constructive interference can
33
only occur when n = 2dsin as shown in Figure 2.3. Hence, XRD can be used to measure d that is the basis of crystallography, an important field of science.1
Incident radiation
Light defracted in phase
O Top plane
A B C
d Second plane
Figure 2.3 Reflection of X-ray from crystal lattice planes. Earlier on, we have been mentioning about the diffraction of X-rays from different planes, it is necessary to designate these planes in a consistent manner. This is done by assigning Miller indices to these lattice planes. Miller indices are represented by (hkl) family of planes. Each reflection of an X-ray from a crystal is assigned a unique hkl value. It is interesting to note that the diffraction peaks are usually broadened when the crystallite is small. Scherrer first treated this particle size broadening and the Scherrer equation4 is given by B(2 ) =
0.94 L cos
where B(2 ) is the full width at half maximum (FWHM) in radians, L is the edge dimension of the crystals and is the wavelength of the radiation. Hence, we can easily obtain the crystallite size from this equation once the FWHM of the most intense peak is known.
34
Although XRD is proved to be very useful in characterizing the crystal structure, it has its own limitations. For the study of materials with preferred orientation, film methods are employed to complement XRD. In addition, more detailed characterization may require specialty instruments such as thin-film camera, texture goniometer or double crystal diffractometer.
2.4.4 Principles of transmission electron microscopy (TEM) The transmission electron microscopy was first developed in the 1930s after wavelength was apparent to play an important role on theoretical resolution. Green light that is used for light microscopy has a wavelength of 0.5 m and therefore a theoretical resolution of about 0.2 m. As we move towards the shorter wavelength of the electromagnetic spectrum, it will pass blue and violet into the range of ultraviolet (< 0.4 m). This means that an ultraviolet microscopy should have a theoretical resolution of 0.05 m and could be used in TEM. However, ultraviolet light can absorb by glass, and the lenses have to be made from quartz. This certainly makes the microscopy extremely expensive and fragile for only a moderate increase in resolution. X-ray microscopy is better in resolution but x-ray cannot be easily refracted to form an image. Electron waves offer the best alternative. The electron being a charged particle can be easily refracted in a magnetic field. Moreover, it can be accelerated by an electric potential. The stronger the potential the faster the electrons will move, and as described by the de Broglie relationship, the shorter the wavelength therefore the better resolution:
h m
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In a typical transmission electron microscopy, the electrons that are high in energy are generated at the gun chamber. These electrons are produced by a tungsten filament, a LaB6 crystal or a field emission gun. The generated beam of electrons is then collimated by magnetic lenses and allowed to pass through the specimen under high vacuum.5 This results in the diffraction pattern that contains transmitted beam and a number of diffracted beams, which will then form images on a fluorescent screen below the specimen. In this case, one can obtain the lattice spacing and symmetry information for the structure under consideration.5 On the other hand, the transmitted beam or one of the diffracted beams can also form magnetic image of the sample on the viewing screen. These bright- and dark-field imaging modes can give information about the size and shape of the microstructural or nanostructural constituents of the materials. One can obtain the high-resolution image that contains information on the atomic structural of the materials if the transmitted beam and one or more diffracted beams are to recombine. It seems that TEM offers much help in the study of local structure, morphology and chemistry of material in extremely high resolution.5 Nonetheless, TEM requires the preparation of samples that could be time consuming. In addition, there are some materials especially polymers that lose their crystallinity and mass upon interaction with strong electron beam. Imaging resolution is limited to about 0.2 nm because of the great difficulties in manipulating the magnetic field to get a higher resolution.
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2.4.5 Principles of inductively coupled plasma-atomic emission spectroscopy (ICPAES) ICP-AES is commonly employed to determine the concentration of elements in solution. The main advantage of ICP-AES is the ability to analyze many elements, either simultaneously or in a rapid sequential manner. This depends a lot on the type of instrument being used. The principle of ICP-AES is based on the different emission energy that is specific for different element. As shown in Figure 2.4, the liquid sample is first atomized by a nebulizer into a stream of argon gas that carried the gaseous atoms into the plasma. The plasma will then thermally excite the elements in the solution. Upon relaxing back to their ground state, these excited elements will release photons that can be detected by photomultiplier tubes. The number of photomultiplier tubes used depends on the type of instrument. The instrument meant for simultaneous system utilizes photomultipliers tubes positioned at predetermined wavelengths on a focal curve with one photomultiplier tube for each element. On the other hand, the instrument for sequential system has only one photomultiplier tube with a computer controlled grating that rotates to focus preprogrammed regions of the spectrum on the exit slit. The intensity of the signal obtained at the end corresponds to the concentration of the elements.
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Figure 2.4 Schematics of typical ICP instrument with scanning monochromator. ICP-AES share many similar advantages as atomic absorption techniques such as analysis of many types of samples and very good detection limit. The most important advantage of ICP-AES is the ability to analyze many elements in one go. This certainly helps to save a great deal of analysis time. Furthermore, ICP-AES also allows quantitative analysis over a wide concentration range thus making the determination of major and trace component possible without dilution. However, ICP-AES has it own limitations such as spectral overlap and matrix effect. Spectral overlap is caused by the direct overlap of the emission lines from the analyte and the interfering element. This can be avoided by taking an alternate line only in a sequential instrument. Matrix effects, on
38
the other hand, affect the sensitivity of this analysis method by changing the efficiency of nebuliztion. Only though matching the matrix of the standard with that of the sample can help to minimize some of these matrix effects.
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2.5 References 1. Robinson, J. W. Undergraduate Instrumental Analysis 5th Edition, Marcel Dekker, Inc., New York, 1995. 2. Chen, W. S.; Sommers, J. M. J. Phys. Chem. B 2001, 105, 8816. 3. Murphy, N. S.; Reidinger, F. A Guide to Materials Characterization and Chemical Analysis 2nd edition, VCH publishers, Inc., New York, 1996. 4. Bradley, J. S. Clusters and Colloids, VCH, Weinhein, 1994. 5. Macur, J. E.; Marti, J.; Lui, S. C. A Guide to Materials Characterization and Chemical Analysis 2nd edition, VCH publishers, Inc., New York, 1996.
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Chapter 3 Facile synthesis of high-quality CdS, ZnS and ZnxCd1-xS nanocrystals using metal salts and elemental sulfur
3.1 Introduction Semiconductor nanocrystals are of great interest for both fundamental research and technical applications as a consequence of the large surface-to-volume ratio and the three-dimensional quantum confinement of excitons.1-6 Among various semiconductor materials, the binary cadmium chalcogenides have been the most frequently studied due to their size-dependent photoluminescence (PL) tunable across the visible spectrum. Also, the relevant ternary compounds ZnxCd1-xS are promising materials for high density optical recording devices, blue or even ultraviolet laser diodes, and photovoltaic cells.7-8 The lack of adequate synthetic methods for producing the desired high-quality nanocrystals is still a bottleneck in this field. Since the introduction of the high temperature organometallic approach and various alternatives, the synthetic approaches to CdSe nanocrystals have been well developed.9-12 Through these synthetic procedures, CdSe nanocrystals are produced with a size distribution of 5-10% relative standard deviation without any size selection and the room temperature quantum yields (QYs) of 30-80% for most of the visible spectral range. In comparison, the synthesis of CdS nanocrystals is not as advanced. Conventionally, arrested precipitation from simple inorganic ions in solutions has been utilized to prepare CdS.13-15 Recently, several groups have already reported the synthesis of sulfide nanocrystals by thermolysis of single source precursors.16-18 Qian and co-workers developed a solvothermal method to obtain
41
many kinds of semiconductors including CdS.19-20 Although most of these developed methods for synthesizing CdS are of widespread importance, there are still some limitations to their utilities. For example, the resulting quantum yields are not very high, or the particle size distributions are relatively broad. Moreover, toxic, unstable or pyrophoric agents are employed such as H2S, bis(trimethylsilyl)sulfide (TMS)2S or Cd(CH3)2. Recently, Peng et al. reported the synthesis of cadmium chalcogenide nanocrystals through a chemical approach using CdO or Cd-phosphonic acid as Cd precursor and using non-coordinating solvents.10, 21 In this chapter, a green chemical route to produce high-quality CdS, ZnS and ZnxCd1-xS nanocrystals is reported. And this green chemical route means safe, simple, inexpensive, reproducible, versatile and user friendly. The controllable and narrow size distributions have a relative standard deviation of 7-11%. The obtained CdS and ZnxCd1xS
nanocrystals possess quantum-confinement wavelength-tunable optical absorption and
band-edge emission with high quantum yields of 25-45%. The PL spectra are dominated by the band-edge emission without the broad emission from deep traps. Furthermore, it is a one-pot method using stable, commonly available precursors (metal salts such as metal stearate, acetate, chloride, and sulfate etc. as the cadmium source and elemental sulfur as the sulfide source). The coordinating solvents used in this study include a series of convenient high-boiling point long-chain amines such as hexadecylamine, oleylamine, etc. Our research focuses mainly on the formation of cubic zinc-blende CdS and ZnxCd1xS
nanocrystals at elevated temperature in this synthesis approach, and the rapid
nucleation and instant termination of the crystal growth process is observed. This
42
nucleation and growth feature makes the reproducible and controllable synthesis of nanocrystals with specific emission wavelength feasible.
3.2 Experimental section 3.2.1 Materials Cadmium acetate (Cd(Ac)2, 98%), cadmium sulfate (CdSO4, 99%), cadmium chloride (Cd(Cl)2, 99.99%), zinc stearate (Zn(ST)2, 90%), 1-hexadecylamine (HDA, 90%), dodecylamine (98%) and sulfur powder (99.98%) were purchased from Aldrich. Cadmium stearate (Cd(ST)2, 90%) was purchased from Strem Chemicals. Methanol, toluene, chloroform and acetone were purchased from Merck. Carbon-coated copper grids (200 mesh) for preparing TEM specimens were purchase from Ted Pella Inc.
3.2.2 Synthetic methods Typically, a mixture of 68.1 mg Cd(ST)2 (0.1 mmol) and 3.5 g technical-grade HDA is heated to 290 oC under argon flow. 1.0 ml solution of sulfur (1.6 mg, 0.05 mmol) in dodecylamine is then swiftly injected into this solution. The reaction mixture is kept at 280 oC for the growth/annealing of the nanocrystals while monitoring the evolution of the absorption and PL emission spectra. During the growth stage, aliquots are taken at different time intervals and UV-vis and PL spectra are recorded for each aliquot. The insoluble dark solid, if existing, is separated by centrifugation and decantation prior to any further measurements. XRD and TEM measurements are also performed in order to characterize the crystallinity, size, and size distribution of the resulting particle samples. All the measurements are performed on the original aliquots without any size-selection.
43
A similar fashion is adopted for the synthesis of CdS nanocrystals using other Cd precursors (such as Cd(Ac)2, CdSO4 or CdCl2). ZnS nanocrystals are also prepared with this synthetic approach by using the corresponding Zn precursor, while an equimolar amount of Zn and S precursors are used. The preparation method for ternary ZnxCd1-xS alloyed nanocrystals is similar to that for the binary CdS. Cd and Zn precursors are with different molar ratios and the injected amount of sulfur is equal to the total molar amount of the Cd and Zn precursors.
3.2.3 Characterization All the resulting samples are immediately cooled and diluted with chloroform. The UV-vis and PL spectra of the nanocrystals are recorded promptly. The room-temperature PL efficiencies are determined by comparing the integrated emission of the samples to that of dyes in solutions with identical optical density at the excitation wavelength. The excitation wavelengths are set at the first absorption peak of the measured QDs. The dyes (such as rhodamine 6G, rhodamine 640 or coumarin 540) should have significant overlaps in their PL spectra with those of the QDs to be measured. A quadratic refractive index correction is done if two different solvents are used to dissolve QDs and dyes. Also the known efficiencies of the QDs in chloroform can be used to measure the efficiencies of other QDs by comparing their integrated emission or PL intensity in solution. A low concentration of the solutions is used to avoid obvious reabsorption. The UV-vis absorption spectra are recorded on a Shimadzu UV-1601 scanning spectrophotometer operating at a slit width of 1.0 nm. Bandgap energy determinations are made by analyzing the absorption data using the method outlined by Fendler and co-workers to
44
extract the value for the absorption onset. Photoluminescence spectra are acquired on a Shimadzu RF-5301PC spectrometer. Emission spectra are taken using an excitation wavelength of = 300 nm with excitation and emission slit widths set at 2.0 nm. A mixed solvent of methanol and acetone is used to precipitate the resulting nanocrystals in chloroform solution, which are then isolated by centrifugation and decantation. Samples are prepared by placing a diluted solution of nanocrystals in chloroform onto carbon-coated copper grids and allowing them to dry in a vacuum desiccator overnight. The excess ligands and reaction precursors are removed by extensive purification prior to high solution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD) and inductively coupled plasma atomic emission (ICP) measurements. No further size-selective purification is done for the samples. A JEOL JEM3010 transmission electron microscope (operated at an accelerating voltage of 300 kV) is used to analyze the size, size distribution, and structure of the resulting nanocrystals, which are deposited on carbon-coated copper grids using the QD hexane solutions. The size distribution histograms for all the samples are obtained by analyzing over 200 crystallites in each sample. The XRD patterns of the final products are recorded by a Siemens D5005 X-ray powder diffractometer. The composition of the obtained ZnxCd1-xS nanocrystals is measured by means of ICP by a standard HCl/HNO3 digestion. The mean particle sizes for some samples of CdS and ZnxCd1-xS nanocrystals are determined by transmission electron microscopy, and found to be in good agreement with the values estimated from the excition absorption peaks. Considering the aim of our work, UV-vis absorption spectroscopy is a more convenient technique to estimate the mean diameters of nanocrystal in colloidal suspensions, because it has the important advantages
45
of probing the whole ensemble used for the quantum yield and lifetime measurements and allowing for the analysis of the crude samples. Photoluminescence quantum yields (QY) are obtained by comparing with a standard dye (Coumarin 540) and using data collected from the luminescence and the absorption spectra as follows:
1 TST QY = 1T x
X ST
q ST
where TST and TX are the transmittances at = 400 nm for the standard and the sample, respectively, and qST is the quantum yield of the standard (98% as indicated by the supplier, Aldrich). The term X and ST give the integrated emitted photon fluxes (photons s-1) for the sample and the standard, respectively. Utmost care is taken to ensure a constant and reproducible position for the sample/standard holder and unchanged instrumental conditions throughout the whole measurement process. The values of X and ST are determined from the photoluminescence spectra corrected for the instrumental response, by integrating the emission intensity over the desired spectral range. Only the band-edge luminescence peak is integrated (any other luminescence bands are discarded as background). Correction for the luminescence reabsorption is performed, based on the Lambert-Beer law, but is found to be unnecessary for optical densities 0.1 . The accuracy of the method is calculated to be 10% , based on remeasurements.
46
3.2.4 Synthesis of high-quality CdS, ZnS and ZnxCd1-xS nanocrystals 3.2.4.1 Synthesis of CdS nanocrystals 0.1 mmol (68 mg) Cd(ST)2 is dissolved in 3.5 g technical-grade HDA. The mixture is heated to 295 oC under argon flow. Then 0.05 mmol sulfur is swiftly injected into this solution. The reaction mixture is then kept at 280 oC for the growth/annealing of the nanocrystals.
PL Intensity (a.u.)
10 sec 2 min 10 min 30 min
350
400
450
500
550
Absorbance (a.u.)
300
350
400
450
500
Wavelength / nm
Wavelength / nm
Figure 3.1 Photoluminescence (Left) and UV-vis spectra for CdS nanocrystals prepared from Cd(ST)2. The photoluminescence spectrum of the CdS nanocrystals (Figure 3.1) shows a very narrow emission bandwidth (FWHM = 26 nm) with an emission maximum at = 450 nm.
47
111
Intensity (a.u.)
220
311
20
30
40
50
60
2 Theta
Figure 3.2 Powder X-ray diffraction pattern of CdS nanocrystals prepared from Cd(ST)2. As shown in Figure 3.2, the XRD pattern of the CdS nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes. These peaks correspond to the signatures for the cubic (zincblende) structural form. And the intensity of the (111) orientation is predominant.
3.2.4.2 Synthesis of ZnS nanocrystals. 0.1 mmol (63 mg) Zn(ST)2 is dissolved in 3.5 g technical-grade HDA. The mixture is heated to 288 oC under argon flow. Then 0.1 mmol sulfur is swiftly injected into this solution. The reaction mixture is then kept at 280 oC for the growth/annealing of the nanocrystals.
48
PL Intensity (a.u.)
350
400
450
500
550
Absorbance (a.u.)
10 sec 30 sec 2 min 5 min 10 min
300
350
400
450
500
Wavelength / nm
Wavelength / nm
Figure 3.3 Photoluminescence (Left) and UV-vis spectra for ZnS nanocrystals prepared from Zn(ST)2. The photoluminescence spectrum of the ZnS nanocrystals (Figure 3.3) shows an emission maximum at = 347 nm.
111
Intensity (a.u.)
220
311
20
30
40
50
60
2 Theta
Figure 3.4 Powder X-ray diffraction pattern of ZnS nanocrystals prepared from Zn(ST)2.
As shown in Figure 3.4, the XRD pattern of the ZnS nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes. These
49
peaks correspond to the signatures for the cubic (zincblende) structural form. And the intensity of the (111) orientation is predominant.
3.2.4.3 Synthesis of ternary alloyed Zn0.17Cd0.83S nanocrystals 0.1 mmol (68 mg) Cd(ST)2 and 0.05 mmol (31.5 mg) Zn(ST)2 are mixed and dissolved in 3.5 g technical-grade HDA. The mixture is heated to 267 oC under argon flow. Then 1.0 ml solution of sulfur in dodecylamine is swiftly injected into this solution. The injected amount of sulfur (4.8 mg, 0.15 mmol) is equal to the total molar amount of Zn and Cd precursors. The reaction mixture is then kept at 260 growth/annealing of the nanocrystals.
o
C for the
PL Intensity (a.u.)
Absorbance (a.u.)
350
400
450
500
550
300
350
400
450
500
550
Wavelength / nm
Wavelength / nm
Figure 3.5 Photoluminescence (Left) and UV-vis spectra for Zn0.17Cd0.83S nanocrystals. The photoluminescence spectrum of the Zn0.17Cd0.83S nanocrystals (Figure 3.5) shows an emission bandwidth (FWHM = 31 nm) with an emission maximum at = 452 nm.
50
111
Intensity (a.u.)
220 311
20
30
40
50
60
2 Theta
Figure 3.6 Powder X-ray diffraction pattern of Zn0.17Cd0.83S nanocrystals.
As shown in Figure 3.6, the XRD pattern of the Zn0.17Cd0.83S nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes. These peaks correspond to the signatures for the cubic (zincblende) structural form. And the intensity of the (111) orientation is predominant.
3.2.4.4 Synthesis of ternary alloyed Zn0.23Cd0.77S nanocrystals 0.1 mmol (68 mg) Cd(ST)2 and 0.1 mmol (63 mg) Zn(ST)2 are mixed and dissolved in 3.5 g technical-grade HDA. The mixture is heated to 270 oC under argon flow. Then 1.0 ml solution of sulfur in dodecylamine is swiftly injected into this solution. The injected amount of sulfur (6.4 mg, 0.2 mmol) is equal to the total molar amount of Zn and Cd precursors. The reaction mixture is kept at 260 oC for the growth/annealing of the nanocrystals.
51
PL Intensity (a.u.)
Absorbance (a.u.)
350
400
450
500
550
300
350
400
450
500
550
Wavelength / nm
Wavelength / nm
Figure 3.7 Photoluminescence (Left) and UV-vis spectra for Zn0.23Cd0.77S nanocrystals. The photoluminescence spectrum of the Zn0.23Cd0.77S nanocrystals (Figure 3.7) shows a narrow emission bandwidth (FWHM = 28 nm) with an emission maximum at = 445 nm.
111
Intensity (a.u.)
220
311
20
30
40
50
60
2 Theta
52
As shown in Figure 3.8, the XRD pattern of the Zn0.23Cd0.77S nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes. These peaks correspond to the signatures for the cubic (zincblende) structural form.
3.2.4.5 Synthesis of ternary alloyed Zn0.28Cd0.72S nanocrystals 0.05 mmol (34 mg) Cd(ST)2 and 0.1 mmol (63 mg) Zn(ST)2 are mixed and dissolved in 3.5 g technical-grade HDA. The mixture is heated to 270 oC under argon flow. Then 1.0 ml solution of sulfur in dodecylamine is swiftly injected into this
solution. The injected amount of sulfur (4.8 mg, 0.15 mmol) is equal to the total molar amount of Zn and Cd precursors. The reaction mixture is kept at 260 oC for the growth/annealing of the nanocrystals.
PL Intensity (a.u.)
350
400
450
500
550
Absorbance (a.u.)
300
350
400
450
500
Wavelength / nm
Wavelength / nm
53
111
Intensity (a.u.)
220 311
20
30
40
50
60
2 Theta
Figure 3.10 Powder X-ray diffraction pattern of Zn0.28Cd0.72S nanocrystals. As shown in Figure 3.10, the XRD pattern of the Zn0.28Cd0.72S nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes. These peaks correspond to the signatures for the cubic (zincblende) structural form.
3.2.4.6 Synthesis of ternary alloyed Zn0.32Cd0.68S nanocrystals 0.05 mmol (34 mg) Cd(ST)2 and 0.15 mmol (94.5 mg) Zn(ST)2 are mixed and dissolved in 3.5 g technical-grade HDA. The mixture is heated to 265 oC under argon flow. Then 1.0 ml solution of sulfur in dodecylamine is swiftly injected into this solution. The injected amount of sulfur (6.4 mg, 0.2 mmol) is equal to the total molar amount of Zn and Cd precursors. The reaction mixture is then kept at 260 growth/annealing of the nanocrystals.
o
C for the
54
PL Intensity (a.u.)
Absorbance (a.u.)
350
400
450
500
550
300
350
400
450
500
Wavelenght / nm
Wavelength / nm
111
Intensity (a.u.)
220
311
20
30
40
50
60
2 Theta
Figure 3.12 Powder X-ray diffraction pattern of Zn0.32Cd0.68S nanocrystals. As shown in Figure 3.12, the XRD pattern of the Zn0.32Cd0.68S nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes.
55
These peaks correspond to the signatures for the cubic (zincblende) structural form. And the intensity of the (111) orientation is predominant.
3.2.4.7 Synthesis of ternary alloyed Zn0.42Cd0.58S nanocrystals 0.05 mmol (34 mg) Cd(ST)2 and 0.2 mmol (126 mg) Zn(ST)2 are mixed and dissolved in 3.5 g technical-grade HDA. The mixture is heated to 267 oC under argon flow. Then 1.0 ml solution of sulfur in dodecylamine is swiftly injected into this solution. The injected amount of sulfur (8.0 mg, 0.25 mmol) is equal to the total molar amount of Zn and Cd precursors. The reaction mixture is kept at 260 oC for the growth/annealing of the nanocrystals.
PL Intensity (a.u.)
350
400
450
500
550
Absorbance (a.u.)
300
350
400
450
500
550
Wavelength / nm
Wavelenght / nm
56
111
Intensity (a.u.)
220 311
20
30
40
50
60
2 Theta
Figure 3.14 Powder X-ray diffraction pattern of Zn0.42Cd0.58S nanocrystals. As shown in Figure 3.14, the XRD pattern of the Zn0.42Cd0.58S nanocrystals reveals three diffraction peaks which can be attribute to the (111), (220) and (311) lattice planes. These peaks correspond to the signatures for the cubic (zincblende) structural form. And the intensity of the (111) orientation is predominant.
3.3 Results and discussion For the synthesis of CdS, ZnS and ZnxCd1-xS nanocrystals, the metal salt is dissolved in amine to form a metal-amine complex at an appropriate high temperature. To the resulting solution, elemental sulfur dissolved in amine is swiftly injected. The reaction mixture is heated at a certain temperature for some period of time to generate the desired metal sulfide nanocrystals. Figure 3.15 displays the temporal evolution of the absorption and the PL spectra of the CdS nanocrystals, which are produced at 280 oC through the reaction of cadmium stearate in HDA with the injected sulfur dissolved in dodecylamine. The growth kinetics
57
of CdS nanocrystals prepared by this new approach possess a similar pattern to that of the CdS nanocrystals formed by the reaction of CdO-hexylphosphonic acid with (TMS)2S in the TOPO/TOP system.10 After the growth/annealing for 1 h at the reaction temperature, the sharp excitonic absorption peaks are still retained, with the narrow band-edge PL emission peak located at 451 nm with a full width at half maximum (fwhm) of 24 nm. The PL quantum yield gradually reaches its maximum value of 30%, and the broad deep-trap emission peaks disappear completely due to the removal of structural defects. These sharp features of the absorption and the PL peaks demonstrate that the size distribution of the resulting nanocrystals is nearly monodisperse. A certain control of the particle size corresponding to the tunable absorption onset and emission wavelength is possible by adjusting the nucleation and growth temperature or the concentration of the reactant precursors.
PL UV-Vis
Absorbance (a.u.)
350
400
450
500
550
wavelength / nm
60 min 30 min 5 min 2 min 1 min 30 sec
300
350
400
450
500
550
600
650
Wavelength / nm
Figure 3.15 Temporal evolution of UV-vis spectra of a growth reaction of CdS nanocrystals at 280 oC. Inset: PL and absorption of a CdS nanocrystal sample.
58
Figure 3.16 TEM images of (a) CdS nanocrystals prepared from Cd(ST)2, (b) CdS nanocrystals from Cd(Ac)2, (c) ZnS nanocrystals from ZnCl2, (d) ZnxCd1-xS nanocrystals. Figure 3.16 shows a TEM micrograph of the as-prepared CdS nanocrystals without any size selection after 1 h growth at the above-mentioned synthesis conditions. Nearly monodisperse particles are observed with an average size of 4.5 0.4 nm in diameter. It is surprising that the X-ray diffraction patterns in Figure 3.17 clearly show a cubic zincblende crystal phase of the obtained CdS nanocrystals prepared at 280 oC all of the peaks match well with the Bragg reflections for the standard cubic CdS structure. As expected, the width of the diffraction peaks is considerably broadened and decreases with increasing particle size. The diameter of the crystallite is related to the width of the Bragg reflection peak in terms of the Scherrer formula: FWHM = (0.94 ) /( L cos B ) where L is the crystal domain size. By using the Scherrer formula, we can calculate the mean sizes of the nanocrystals from the peak width at half-maximum. Particles sizes obtained from the width of the (111) reflection are depicted in Figure 3.17. And at the 59
same time, we use direct TEM observations to confirm our calculation results. It is wellknown that CdS cluster molecules forming single crystals usually display a cubic structure.22-24 and at room temperature the cubic CdS nanocrystals are obtained by using polyphosphate or thioglycerol as the stabilizer.14, 25, 26 However, the hexagonal wurtzite crystal phase of CdS is thermodynamically stable, thus it is the favorite phase at elevated temperature.26 To our best knowledge, almost all of the CdS nanocrystals prepared at such elevated temperature exhibit a hexagonal structure.
ZnS, 4.4 nm Zn0.42Cd0.58S, 4.3 nm
Zn0.32Cd0.68S, 4.6 nm
Intensity (a.u.)
Zn0.28Cd0.72S, 4.2 nm Zn0.23Cd0.77S, 4.3 nm
Zn0.17Cd0.83S, 4.5 nm CdS/Cd(Ac)2, 7.4 nm CdS/Cd(ST)2, 4.1 nm

20 30 40 50 60
2 Theta
Figure 3.17 Powder X-ray diffraction patterns of CdS nanocrystals prepared from Cd(ST)2 or Cd(Ac)2, ZnxCd1-xS alloyed nanocrystals with Zn molar fractions ((a) 0.17, (b) 0.23, (c) 0.28, (d) 0.32, and (e) 0.42), and ZnS nanocrystals from ZnCl2. The stated particles sizes were calculated from the Scherrer equation. The line spectra indicate the reflections of bulk cubic CdS (bottom) and bulk cubic ZnS (top).
60
In addition to Cd(ST)2, the commonly available cadmium salts such as Cd(Ac)2, CdCl2, CdSO4, etc. can also act as cadmium sources when reacting with elemental sulfur to form uniform CdS nanocrystals, while their PL QY is nearly zero. It should be noted that cubic CdS nanocrystals are made by using Cd(Ac)2 or Cd(ST)2, while hexagonal CdS is made by using CdCl2 or CdSO4 as cadmium precursors. Moreover, other high-boiling alkyl amines with different lengths of their alkyl chains such as tetradecylamine and octadecylamine, or unsaturated amine such as oleylamine can also act as coordinating solvents to obtain high-quality nanocrystals. It is based on the consideration of operational convenience that liquid dodecylamine is chosen as the solvent to prepare the sulfur stock solution. The corresponding zinc salts (Zn(ST)2, Zn(Ac)2, ZnCl2, ZnSO4, etc.) and elemental sulfur can also be used to prepare ZnS nanocrystals. Figure 3.16 (b), (c) show the TEM images of the CdS (average size of 7.5 0.5 nm) and ZnS (average size of 4.3 0.4 nm) using Cd(Ac)2 and ZnCl2 as the metal sources respectively. A cubic structure is readily derived for both CdS and ZnS nanocrystals from their corresponding diffractograms (Figure 3.17). The synthetic approach to ternary alloyed ZnxCd1-xS nanocrystals is similar to that for CdS. A certain molar ratio of Cd(ST)2 and Zn(ST)2 are dissolved in HDA to form a clear solution. Then the sulfur stock solution is quickly injected at 270 oC, and the reaction mixture is kept at 260 oC for 0.5 h for the growth/annealing of the nanocrystals. The compositions of the obtained ZnxCd1-xS nanocrystals are analyzed by means of ICP spectroscopy. The ZnxCd1-xS nanocrystals with different Zn molar ratio of (a) 0.17, (b) 0.23, (c) 0.28, (d) 0.32 and (e) 0.42 are obtained from the original reactants with Cd/Zn molar ratios of 2:1, 1:1, 1:2, 1:3 and 1:4, respectively.
61
The TEM image for sample c (average diameter of 4.0 0.4 nm) is shown in Figure 2.16 (d). In fact, the average particle sizes for all the obtained ZnxCd1-xS nanocrystals (sample a, b, c, d and e) are in the range of 3.7 to 4.4 nm as demonstrated by the TEM results. The nearly equal particle size for the alloyed nanocrystals is also displayed by the nearly equal line-width of their corresponding diffraction peaks in the diffractograms (Figure 3.17). Like the binary CdS and ZnS nanocrystals, the diffractograms show that all the alloyed ZnxCd1-xS nanocrystals are of cubic structure as well. In the XRD patterns, as the Zn content increases, the diffraction peaks of the alloyed nanocrystals gradually shift toward larger angles. It is worth noting Vegards Law that for both bulk and thin film alloy materials, the resulting band gap energy Egap is a linear function of the mole fraction x: Ealloy = xEA + (1-x)EB. EA, EB and Ealloy are the band gap energy (or other property) of pure A, pure B, and the alloy AxB1-x, respectively. This law has been successful in predicting the structure and function of many alloyed materials. Our results are consistent with Vegards law, which confirms the formation of alloyed nanocrystals with a homogeneous distribution of compositions.27 The continuous peak-shifting of the monodisperse nanocrystals also rules out phase separation or separate nucleation.
62
460
3.0
Photoluminescence Maximum / nm
(a)
450
b
Bandgap Energy / eV
2.9
(b)
e c
2.8
440
c
430
e
420
a
2.7
410 0.0 0.1 0.2 0.3 0.4 0.5 0.6

0.1 0.2 0.3 0.4 0.5
Molar Composition (% Zn)
Molar Compsotison (% Zn)
Figure 3.18 The Photoluminescence maximum and bandgap energy of the ZnxCd1-xS nanocrystals with different Zn molar ratio of (a) 0.17, (b) 0.23, (c) 0.28, (d) 0.32 and (e) 0.42. The absorption and PL spectra with emission wavelengths centering at = 453, 445, 438, 432 and 421 nm, respectively, of the corresponding ZnxCd1-xS samples a-e are shown in Figure 3.19. The typical fwhm (full width at half maximum) of the PL peaks of the obtained ZnxCd1-xS sample are in the range of 29-38 nm and the room temperature QYs at = 300 nm excitation are 25-45% (calculated by comparing the integrated emission to that of coumarin 540). The PL spectra of all the alloyed ZnxCd1-xS samples are dominated by the band-edge emission with the absence of any broad deep-trap emission peaks. The high QYs, symmetric PL peaks, and narrow spectral widths indicate that the alloyed nanocrystals are homogeneous in compositions with a narrow size distribution, and do not contain pronounced domains of ZnS and/or CdS. Both the first absorption onset in the UV spectra and the band-edge emission peak in the PL spectra shift to shorter wavelength with the increase of the Zn molar ratio in the materials. This observed blue shift (or increase in band-gap energy) is a strong evidence for the formation of alloyed nanocrystals via the intermixing of the wider band-gap ZnS (3.7 eV)
63
with the narrower band-gap CdS (2.5 eV).28 If ZnS nucleates separately, the corresponding PL and absorption peaks should appear. This can rule out the formation of ZnS nanocrystals, which is in agreement with the results of our HRTEM measurement. Evidence for the alloyed structures also comes from the finding that the observed emission wavelength can not be achieved by a binary mixture of CdS or ZnS nanocrystals with the identical particle size.
Absorbance (a.u.)
e d c b a
300
350
400
450
500
550
600
Wavelength / nm
e dc b a
PL Intensity (a.u.)
350
400
450
500
550
Wavelength / nm
Figure 3.19 Absorption (Up) and PL spectra with ex = 300 nm for ZnxCd1-xS nanocrystals with Zn mole fractions of (a) 0.17, (b) 0.23, (c) 0.28, (d) 0.32 and (e) 0.42. The temporal evolution for the PL spectra of the alloyed nanocrystals is very unusual (Figure 3.20). In most reaction systems for producing nanocrystals, a significant spectral wavelength shift is usually observed during the nanocrystals growth/annealing
64
progress at high temperature.9-12, 21 For the studied alloyed nanocrystals, for example, of Zn0.28Cd0.62S (sample c), the wavelengths of the PL peak maximum for the aliquot samples at different time intervals (except the 10 s sample which shows not observed PL emission) are almost fixed at = 438 nm during the 1 h growth/annealing progress at 260
o
C. At the same time, the PL intensity increases steadily to the maximum value for the
0.5 h sample and then decreases gradually. The fixed PL peaks demonstrates that the particles for the investigated period of time keep almost the same size, which is further proved by the TEM results. These results show that the alloyed nanocrystals nucleate rapidly and crystal growth finish/terminate instantly in a time course of less than 20 seconds. This finding is quite different from the behaviors observed from the preparation of nanocrystals by other methods at high temperature, where a rapid nucleation process is commonly accompanied by a certain period of time (a few minutes to hours) for the size-focusing nuclei growth process followed by the size-defocusing Oswald ripening progress.29-31 The instant termination of the growth progress may originate from the strong reducibility of the coordinating solvent (amine) at high temperature to the reactants, i.e., metal salts and sulfur. Furthermore, the corresponding binary CdS and ZnS adopting the same crystal structure may have a contribution to this new behavior of crystal growth. This PL emission wavelength fixation during the particle
growth/annealing progress is an advantage for the reproducible and controllable synthesis of nanocrystals with a specified emission wavelength.
65
438 nm
30 min 60 min 5 min 1 min 20 sec 10 sec
PL intensity (a.u.)
350
400
450
500
550
Wavelength / nm
Figure 3.20 Temporal evolution of PL spectra with ex = 300 nm of a growth reaction of Zn0.28Cd0.72S nanocrystals at 260 oC with an equal precursor concentration.
66
3.4 Conclusions 1. The obtained CdS and ZnxCd1-xS nanocrystals possess quantum-confinement wavelength-tunable optical absorption and band-edge emission with high quantum yields of 25-45%. The PL spectra are dominated by the band-edge emission without the broad emission from deep traps.
2. The alloyed nanocrystals nucleate rapidly and the crystal growth terminates instantly in a time course of less than 20 seconds. This finding is quite different from the behaviors observed from the preparation of nanocrystals by other methods at high temperature, where a rapid nucleation process is commonly accompanied by a certain period of time.
3. The high QYs, symmetric PL peaks, and narrow spectral widths indicate that the alloyed nanocrystals are homogeneous in compositions with a narrow size distribution, and do not contain pronounced domains of ZnS and/or CdS. Both the first absorption onset in the UV spectra and the band-edge emission peak in the PL spectra shift to shorter wavelength with the increase of the Zn molar ratio in the materials. This observed blue shift (or increase in band-gap energy) is a strong evidence for the formation of alloyed nanocrystals via the intermixing of the wider band-gap ZnS with the narrower band-gap CdS.
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3.5 References (1) Alivisatos, A. P. Science 1996, 271, 933. (2) Markovich, G.; Collier, C. P.; Henrichs, S. E.; Remacle, F.; Levine, R. D.; Heath, J. R. Acc. Chem. Res. 1999, 32, 415. (3) Colvin, V. L.; Schlamp, M. C.; Alivisatos, A. P. Nature 1994, 370, 354. (4) Tessler, N.; Medvedev, V.; Kazes, M.; Kan, S. H.; Banin, U. Science 2002, 295, 1506. (5) Bruchez, M.; Moronne, M.; Gin, P.; Weiss, S.; Alivisatos, A. P. Science 1998, 281, 2013. (6) Chan, W. C. W.; Nie, S. M. Science 1998, 281, 2016. (7) Wu, B. J.; Cheng, H.; Guha, S.; Haase, M. A.; DePuydt, J. M.; Meis-Haugen, G.; Qiu, J. Appl. Phys. Lett. 1993, 63, 2935. (8) Guha, S.; Wu, B. J.; Cheng, H.; DePuydt, J. M. Appl. Phys. Lett. 1993, 63, 2129. (9) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 1993, 115, 8706. (10) Peng, Z. A.; Peng, X. G. J. Am. Chem. Soc. 2001, 123, 183. (11) Qu, L. H.; Peng, Z. A.; Peng, X. G. Nano Lett. 2001, 1, 333. (12) Qu, L. H.; Peng, X. G. J. Am. Chem. Soc. 2002, 124, 2049. (13) Spanhel, L.; Haase, M.; Weller, H.; Henglein, A. J. Am. Chem. Soc. 1987, 109, 5649. (14) Vossmeyer, T.; Katsikas, L.; Giersig, M.; Popovic, I. G.; Diesner, K.; Chemseddine, A.; Eychmuller, A.; Weller, H. J. Phys. Chem. 1994, 98, 7665. (15) Sooklal, K.; Hanus, L. H.; Ploehn, H. J.; Murphy, C. J. Adv. Mater. 1998, 10, 1083. (16) Pradhan, N.; Efrima, S. J. Am. Chem. Soc. 2003, 125, 2050.
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(17) Lee, S. M.; Jun, Y. W.; Cho, S. N.; Cheon, J. J. Am. Chem. Soc. 2002, 124, 11244. (18) Lazell, M.; OBrien, P. J. Mater. Chem. 1999, 9, 1381. (19) Yang, J.; Xue, C.; Yu, S. H.; Zeng, J. H.; Qian, Y. T. Angew. Chem. Int. Ed. 2002, 41, 4697. (20) Tang, K. B.; Qian, Y. T.; Zeng, J. H.; Yang, X. G. Adv. Mater. 2003, 15, 448. (21) Yu, W. W.; Peng, X. G. Angew. Chem. Int. Ed. 2002, 41, 2368. (22) Dance, I. G.; Choy, A.; Scudder, M. L. J. Am. Chem. Soc. 1984, 106, 6285. (23) Herron, N.; Calabrese, J. C.; Farneth, W. E.; Wang, Y. Science 1993, 259, 1426. (24) Vossmeyer, T.; Reck, G.; Katsikas, L.; Haupt, E. T. K.; Schulz, B.; Weller, H. Science 1995, 267, 1476. (25) Vossmeyer, Y.; Reck, G.; Schulz, B.; Katsikas, L.; Weller, H. J. Am. Chem. Soc. 1995, 117, 12881. (26) Eychmuller, A. J. Phys. Chem. B 2000, 104, 6514. (27) Furdyna, J. K. J. Appl. Phys. 1988, 64, R29. (28) Zhong, X. H.; Han, M. Y.; Dong, Z. L.; White, T. J.; Knoll, W. J. Am. Chem. Soc. 2003, 125, 8589. (29) Peng, Z. A.; Peng, X. G. J. Am. Chem. Soc. 2001, 123, 1389. (30) Peng, X. G.; Manna, L.; Yang, W. D.; Wickham, J.; Scher, E.; Kadavanich, A.; Alivisatos, A. P. Nature 2000, 404, 59. (31) Donega, C. D.; Hickey, S. G.; Wuister, S. F.; Vanmaekelbergh, D.; Meijerink, A. J. Phys. Chem. B 2003, 107, 489.
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Chapter 4 The synthesis of CdS, ZnS and ZnxCd1-xS composites using bis(diethyldithiocarbamate)-cadmium(II)/zinc(II) compounds as singlesource precursors
4.1 Introduction Colloidal semiconductor nanocrystals (quantum dots, QDs)1-6 are the subject of great interest in recent years and consequently potential applications in optoelectronic devices and as biomedical tags.7-13 Among a variety of semiconductor materials, the binary II-VI nanocrystals have been most intensively investigated.14-19 In the last two decades, the main efforts have been focused on the preparation of different color-emitting binary or core-shell nanocrystals with different particle sizes.1,20 However, the tuning of physical and chemical properties by changing the particle size can cause problems in many applications, in particular, if unstable small particles (less than ~2 nm) are used. Recent advances have led to the exploration of tunable optical properties by changing constituent stoichiometries in mixed ternary nanocrystals.21-23 Zhong and co-workers reported ternary alloyed ZnxCd1-xS nanocrystals with luminescent properties comparable or even better than the best-reported binary CdS-based nanocrystals.24 A color-tunable emission of alloyed ZnxCd1-xS nanocrystals can be achieved by altering the particle composition besides controlling the particle size. Another particularly useful approach to the synthesis of II-VI nanocrystals is the pyrolysis of metal-organic species in tri-noctylphosphine oxide (TOPO).25 In this chapter, a variation of this approach has been successfully developed in which single molecule precursors, mostly based on a carbamate
70
complex, have been used to synthesize ternary alloyed ZnxCd1-xS nanocrystals with tunable optical properties, a better crystalline structure and a homogeneous size distribution.
4.2 Experimental section 4.2.1 Materials Zinc oxide (ZnO, 99%), cadmium oxide (CdO, 99.99%), cadmium hydroxide (Cd(OH)2, 98%), diethylamine (99.5%), carbon disulfide (CS2, 99.9%) and sulfur powder (99.98%) were purchased from Aldrich. Methanol, ethanol, toluene, chloroform and acetone were purchased from Merck. Carbon-coated copper grids (200 mesh) for preparing TEM specimen were purchase from Ted Pella Inc.
4.2.2 Characterization 4.2.2.1 Photoluminescence spectroscopy Photoluminescence spectra are acquired on a Shimadzu RF-5301PC spectrometer. Emission spectra are taken using an excitation wavelength of 300 nm with excitation and emission slit widths set at 2.0 nm. The samples are placed in quartz cuvettes. The wavelength of excitation is indicated in the text and is shorter than the onset of the absorption of a particular sample under study.
4.2.2.2 UV-vis spectroscopy

A Shimadzu UV-1601 spectrophotometer is used to carry out the optical
measurements, with samples placed in quartz cuvettes. Toluene is used as reference for the optical measurements. 71
4.2.2.3 X-ray diffraction

X-ray diffraction patterns are measured on a Siemens D5005 X-ray powder
diffractometer. Samples are supported on glass slides. A concentrated suspension of the nanocrystals is slowly evaporated at room temperature on to the glass slide to obtain a sample for the analysis.
4.2.2.4 Electron microscopy A JEOL JEM3010 transmission electron microscope (operated at an accelerating voltage of 300 kV) is used to analyze the size, size distribution, and structure of the resulting nanocrystals, which are deposited on carbon-coated copper grids using the QD toluene solutions. The excess solvent is removed with a paper tip and the samples are allowed to dry completely at room temperature over night.
4.2.3 Synthetic methods

4.2.3.1 Synthesis of zinc bis(diethyldithiocarbamate)
Zn(S2CNEt2)2 is synthesized according to the literature method.26 A mixture of zinc hydroxide (4.2 g, 42.3 mmol), diethylamine (5 g, 68.4 mmol) and carbon disulfide (5 cm3, 83.3 mmol) is suspended in ethanol and stirred at ca 70 C for 2 hours and then left to cool. The reaction mixture is filtered and the crude white product is recrystallized from acetone (Yield: 10.42 g, 34.3 mmol, 78%).
72
4.2.3.2 Synthesis of cadmium bis(diethyldithiocarbamate) The method to synthesize Cd(S2CNEt2)2 is a modification of a recipe from the literature.27 A mixture of cadmium hydroxide (8.43 g, 46.2 mmol), diethylamine (7.3 g, 100 mmol) and carbon disulfide (5 cm3, 83.3 mmol) in ethanol is refluxed for 1 hour. The mixture is filtered to remove the solid impurities and the clear filtrate is evaporated under vacuum. The white solid product is recrystallized from chloroform at room temperature to give Cd(S2CNEt2)2 (Yield: 14.11 g, 40.2 mmol, 73%).
Figure 4.1 Schematic representation of the growth of nanocrystals.
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4.2.3.3 Synthesis of CdS nanocrystals In a typical synthesis, Cd(S2CNEt2)2 (41mg) is fully dissolved in tri-noctylphosphine (TOP) (0.5 ml). This solution is then quickly injected into hot (300 C) solution of tri-n-octylphosphine oxide (TOPO) (1.5 g) and hexadecylamine (HDA) (1.5 g) and keeps at this temperature for 30 minutes to produce CdS nanocrystals.
10 min 20 min 30 min
PL Intensity (a.u.)
450
500
550
600
650
Absorbance (a.u.)
300
400
500
600
700
800
Wavelength / nm
Wavelength / nm
Figure 4.2 Photoluminescence (Left) and UV-vis spectra for CdS nanocrystals. The photoluminescence spectrum of the CdS nanocrystals (Figure 4.2) shows a very narrow emission bandwidth (FWHM = 28 nm) with an emission maximum at = 536 nm. This is consistent with the previously reported photoluminescence behavior for CdS synthesized by a similar method with the emission attributed to the band-band electronhole recombination.24
74
110 002
112
Intensity (a.u.)
103
20
30
40
50
60
2 Theta
Figure 4.3 Powder X-ray diffraction pattern of CdS nanocrystals.
The observed peaks in the diffraction pattern (Figure 4.3) can be assigned to a hexagonal phase more readily than to a cubic one with the (002), (110), (103) and (112) planes of the wurtzite phase being obviously visible. Furthermore, the (002), (110) and (112) planes are indexed confirming the hexagonal phase.
4.2.3.4 Synthesis of ZnS nanocrystals Zn(S2CNEt2)2 (38 mg) is dissolved in tri-n-octylphosphine (TOP) (0.5 ml). This solution is then injected into hot (300 C) solution of tri-n-octylphosphine oxide (TOPO) (1.5 g) and hexadecylamine (HDA) (1.5 g) and keeps at this temperature for 30 minutes to produce ZnS nanocrystals.
75
PL Intensity (a.u.)
350
400
450
500
550
Absorbance (a.u.)
300
400
500
600
700
800
Wavelength / nm
Wavelength / nm
Figure 4.4 Photoluminescence (Left) and UV-vis spectra for ZnS nanocrystals. The photoluminescence spectrum of the ZnS nanocrystals (Figure 4.4) shows an emission maximum at = 345 nm. Accurate measurements of the absorption edge of ZnS nanocrystals are difficult owing to the overlap with the TOPO absorption at = 300 nm.
002
Intensity (a.u.)
110
112
103
20
30
40
50
60
2 Theta
Figure 4.5 Powder X-ray diffraction pattern of ZnS nanocrystals.
The resulting XRD pattern of ZnS (Figure 4.5) shows broad peaks along the (002), (110), (103) and (112) planes that were assigned to a hexagonal phase.
76
4.2.3.5 Synthesis of ternary alloyed Zn0.4Cd0.6S nanocrystals Cd(S2CNEt2)2 (20 mg) and Zn(S2CNEt2)2 (18 mg) are both dissolved in tri-noctylphosphine (TOP) (0.5 ml). This solution is then injected into a hot (300 C) solution of tri-n-octylphosphine oxide (TOPO) (1.5 g) and hexadecylamine (HDA) (1.5 g) and keeps at this temperature for 30 minutes to produce Zn0.4Cd0.6S nanocrystals. The composition of this obtained ZnxCd1-xS nanocrystals is measured by means of inductively coupled plasma emission spectroscopy (ICP) by a standard HCl/HNO3 digestion.
PL Intensity (a.u.)
350
400
450
500
550
600
Absorbance (a.u.)
300
400
500
600
Wavelength / nm
Wavelength / nm
Figure 4.6 Photoluminescence (Left) and UV-vis spectra for Zn0.4Cd0.6S nanocrystals. The photoluminescence spectrum of the Zn0.4Cd0.6S nanocrystals (Figure 4.6) shows an emission maximum at = 473 nm and the absorption band edge at = 446 nm. The emission maximum is close to the band edge emission. The FWHM is 29 nm which suggests a homogeneous size distribution for the nanocrystals.
77
002 110 112
Intensity (a.u.)
103
20
30
40
50
60
2 Theta
The (002), (110), (103) and (112) planes of the wurtzite structure are clearly distinguished in the pattern (Figure 4.7).
4.3 Results and discussion During the reaction process, the composition of the resulting nanocrystals is determined by the Cd/Zn molar ratio and by the different intrinsic Cd and Zn reactivities toward sulfur. The intrinsic reactivities are difficult to change without altering the experimental conditions. Ternary nanocrystals with a wide range of compositions can be prepared by simply controlling the Cd/Zn ratio in the reaction mixture. A key concept is that the quantum dot composition is determined only by the relative formation rates of CdS and ZnS, not by the absolute sulfur concentration in the reaction mixture. The reason is that sulfur is a common species in both CdS and ZnS, so its effect can be canceled out in the kinetic equations describing the relative CdS and ZnS reaction rates. Thus, the nanocrystal composition is expected to remain constant during the whole reaction process, yielding a homogeneous alloy that is uniform from the particle core to the surface. 78
4.3.1 Optical properties In this part, the optical properties of the ternary alloyed ZnxCd1-xS nanocrystals are compared to those of organically capped binary CdS and ZnS nanocrystals. The photoluminescence and absorption spectra for CdS, Zn0.4Cd0.6S and ZnS nanocrystals are shown in Figure 4.8 and 4.9, respectively. The band edge emission peak of the Zn0.4Cd0.6S structure ( = 473 nm) is blue shifted (63 nm) as compared to the CdS nanocrystals ( = 536 nm). The band-edge emission peak of ZnS nanocrystals ( = 345 nm) is consistent with its bulk band gap.
(c)
(b)
(a)
PL Intensity (a.u.)
300
350
400
450
500
550
600
650
Wavelength / nm
Figure 4.8 Photoluminescence spectra of (a) CdS, (b) Zn0.4Cd0.6S and (c) ZnS nanocrystals.
79
Absorbance (a.u.)
(a) (c) (b)
300
400
500
600
700
800
Wavelength / nm
Figure 4.9 Absorption spectra of (a) CdS, (b) Zn0.4Cd0.6S and (c) ZnS nanocrystals. This observed continuous shift of the absorption and PL spectra of the obtained nanocrystals with different compositions is the most direct evidence for the alloying process. With the increase of the Zn mole fractions, a systematical blue shift (or increase in the band-gap energy) is observed for both the first excitonic absorption onsets and the band-edge emission peaks of the resulting nanocrystals. The blue shift of 63 nm of Zn0.4Cd0.6S nanocrystals relative to the CdS is indicative of an alloyed structure via intermixing the wider bandgap ZnS (3.6 eV) with the narrower bandgap CdS (2.6 eV), rather than forming separate CdS, ZnS, or core-shell structured nanocrystals. If CdS or ZnS nucleates separately, their corresponding PL and absorption peaks of the CdS and ZnS nanocrystals should appear respectively. But only single PL and absorption peaks of the resulting nanocrystals are observed in our reaction system. This rules out the possibility of separate nucleation. The TEM and XRD measurements are consistent with our conclusion. If a core-shell structure is formed, a red shift of the optical spectra can be observed as compared to the CdS nanocrystals. The red shift in the absorption spectra of
80
the core/shell nanocrystals in relation to the parent materials are attributed to relaxation of quantum confinement resulting from the growth of the shell.28
PL max.(473 nm)
Absorbance / PL Intensity (a.u.)
Band edge (446 nm)
300
400
500
600
Wavelength / nm
Figure 4.10 Optical absorption spectrum and photoluminescence spectrum showing the band edge and emission maximum of Zn0.4Cd0.6S nanocrystals. The measured photoluminescence spectrum (Figure 4.10) shows an emission maximum close to the absorption band edge in Zn0.4Cd0.6S nanocrystals, and this indicated that band-edge emission was predominant for the luminescence. The surface states or defects normally associated with semiconductor nanocrystals were passivated by TOPO, so the broad deep trap emission associated with these states was absent.
4.3.2 Structure properties Powder X-ray diffraction (XRD) of the nanocrystals reveals a crystalline wurtzite hexagonal structure of the ternary alloyed nanocrystals (Figure 4.11). The characteristic XRD patterns of the alloyed nanocrystals exhibit 7 prominent peaks, which are indexed to the scattering from (100), (002), (101), (102), (110), (103) and (112) planes, respectively.29 Broadened due to the finite nanocrystalline domain size, the wurtzite
81
patterns of nanocrystals contain four peaks (a singlet peak at low angle and a triplet of peaks at high angle) whereas zinc blende patterns from nanocrystals only have two peaks (a singlet at low angle and a singlet at high angle).30-32 The resulting XRD pattern of ZnxCd1-xS shows broad peaks along the (110), (103) and (112) planes that are assigned to a hexagonal phase. The wurtzite structure is kinetically favored and is observed for ZnxCd1-xS nanocrystals, ruling out the possibility of a phase change in the alloyed nanocrystals. The XRD peaks also shift to larger angles gradually as the Zn content increased (Figure 4.11). This continuous peak shifting of the nanocrystals may also rule out phase separation or separated nucleation of CdS or ZnS nanocrystals. The enhanced intensity of the (002) reflection arising from a preferred orientation can be attributed to the extended growth of (002) faces, in contrast to earlier studies where more rapid crystal growth along (002) leads to rod-shape morphologies.33, 34 As we know, such a sharp peak is not available in core-shell structured nanocrystals; thus it provides additional information to more accurately determine the lattice spacing of alloyed ZnxCd1-xS nanocrystals.
(c)
Intensity (a.u.)
(b)
(a)
20
30
40
50
60
2 Theta
Figure 4.11 XRD patterns showing the hexagonal phase for (a) CdS, (b) ZnxCd1-xS and (c) ZnS nanocrystals.
82
50 nm
5 nm
5 nm
Figure 4.12 TEM images of CdS nanocrystals.
83
Average Dimater = 4.2 nm

35 30
Frequency (%)
25 20 15 10 5 0 3.0 3.5 4.0 4.5 5.0 5.5
Diameter (nm)
Figure 4.13 Particle size distributions of CdS nanocrystals. TEM images and particle size distribution histograms for CdS are shown in Figure 4.12 and 4.13, respectively. The TEM micrographs show well-defined, spherical particles and the average particle size diameter is 4.2 nm 10%.
20 nm
5 nm
Figure 4.14 TEM images of ZnS nanocrystals.
84
Average Diameter = 5.1 nm

30
25
20
Frequency (%)
15
10
0 3 4 5 6 7
Diameter (nm)
Figure 4.15 Particle size distributions of ZnS nanocrystals. TEM images and particle size distribution histograms for ZnS are shown in Figure 4.14 and 4.15, respectively. The TEM micrographs show well-defined, spherical particles and the average particle size diameter is 5.1 nm 11%.
85
50 nm
5 nm
5 nm
Figure 4.16 TEM images of Zn0.4Cd0.6S nanocrystals.
86
Average Diameter = 6.1 nm

35
30
Frequency (%)
25
20
15
10
0 4.8 5.6 6.4 7.2 8.0
Diameter (nm)
Figure 4.17 Particle size distributions of Zn0.4Cd0.6S nanocrystals. TEM images and particle size distribution histograms for Zn0.4Cd0.6S are shown in Figure 4.16 and 4.17, respectively. The TEM micrographs show well-defined, spherical particles and the average particle size diameter is 6.1 nm 7%. This increase of average particle size diameter in relation to the parent materials is due to the predominant nucleation of the alloyed nanocrystals.
87
4.4 Conclusions 1. The composition of nanocrystals is determined only by the relative formation rates of CdS and ZnS, not by the absolute sulfur concentration in the reaction mixture. The nanocrystal composition is expected to remain constant during the whole reaction process, yielding a homogeneous alloy that is uniform from the particle core to the surface.
2. This observed continuous shift of the absorption and PL spectra of the obtained nanocrystals with different compositions is the most direct evidence for the alloying process. With the increase of the Zn mole fractions, a systematical blue shift (or increase in the band-gap energy) is observed for both the first excitonic absorption onsets and the band-edge emission peaks of the resulting nanocrystals.
3. The resulting XRD pattern of ZnxCd1-xS show broad peaks along the (110), (103), and (112) planes that are assigned to a hexagonal phase. The wurtzite structure is kinetically favored and is observed for ZnxCd1-xS nanocrystals, ruling out the possibility of a phase change in the alloyed nanocrystals.
88
4.5 Future works In this thesis, we have studied comprehensively into metal sulfide nanoparticles. Nonetheless, all these studies have proven to be fundamental and we have not looked into the application aspect of these materials. In fact, it has been reported that multicolor nanocrystals can be incorporated into small polymer beads and should find broad applications in gene expression studies, high-speed screening, and medical diagnostics. We propose to conduct more studies to look into the application of our materials.
It is known that the shape and size of inorganic nanocrystals could significantly affect their optical and electrical properties. Hence, there will be scientific and technological interests for us to achieve better size and shape control of these alloyed nanocrystals with high quantum yield and stability. Such studies could be realized by adding special coordinating surfactants which have selective adhesion onto certain facets of the formed nanocrystals.
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4.6 References (1) Henglein, A. Chem. Rev. 1989, 89, 1861. (2) Haggata, S. W.; Cole-Hamilton, D. J.; Fryer, J. R. J. Mater. Chem. 1997, 7, 1969. (3) Weller, H. Adv. Mater. 1993, 5, 88. (4) Steigerwald, M. L.; Brus, L. E. Acc. Chem. Rev. 1990, 23, 183. (5) Wang, Y.; Herron, N. J. Phys. Chem. 1991, 95, 525. (6) Green, M.; OBrien, P. Adv. Mater. Opt. Electr. 1997, 7, 277. (7) Han, M. Y.; Gao, X. H.; Su, J. Z.; Nie, S. M. Nat. Biotechnol. 2001, 19, 631. (8) Chan, W. C. W.; Nie, S. M. Science 1998, 281, 2016. (9) Colvin, V. L.; Schlamp, M. C.; Alivisatos, A. P. Nature 1994, 370, 354. (10) Tessler, N.; Medvedev, V.; Kazes, M.; Kan, S. H.; Banin, U. Science 2002, 295, 1506. (11) Sun, S. H.; Murray, C. B.; Weller, D.; Folks, L.; Moser, A. Science 2000, 287, 1989. (12) Bruchez, M.; Moronne, M.; Gin, P.; Weiss, S.; Alivisatos, A. P. Science 1998, 281, 2013. (13) Klimov, V. I.; Mikhailovsky, A. A.; Xu, S.; Malko, A.; Hollingsworth, J. A.; Leatherdale, C. A.; Eisler, H. J.; Bawendi, M. G. Science 2000, 290, 314. (14) Peng, X. G.; Schlamp, M. C.; Kadavanich, A. V.; Alivisatos, A. P. J. Am. Chem. Soc. 1997, 119, 7019. (15) Peng, Z. A.; Peng, X. G. J. Am. Chem. Soc. 2001, 123, 183. (16) Dabbousi, B. O.; Rodriguez-Viejo, J.; Mikulec, F. V.; Heine, J. R.; Mattoussi, H.; Ober, R.; Jensen, K. F.; Bawendi, M. G. J. Phys. Chem. B 1997, 101, 9463. (17) Hines, M. A.; Guyot-Sionnest, P. J. Phys. Chem. 1996, 100, 468.
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(18) Yu, W. W.; Peng, X. G. Angew. Chem. Int. Ed. 2002, 41, 2368. (19) Qu, L. H.; Peng, X. G. J. Am. Chem. Soc. 2002, 124, 2049. (20) Alivisatos, A. P. Science 1996, 271, 933. (21) Kulkarni, S. K.; Winkler, U.; Deshmukh, N.; Borse, P. H.; Fink, R.; Umbach, E. Appl. Surf. Sci. 2001, 169, 438. (22) Harrison, M. T.; Kershaw, S. V.; Burt, M. G.; Eychmller, A.; Weller, H.; Rogach, A. L. Mat. Sci. Eng. B 2000, 69, 355. (23) Korgel, B. A.; Monbouquette, H. G. Langmuir 2000, 16, 3588. (24) Zhong, X. H.; Feng, Y. Y.; Knoll, W.; Han, M. Y. J. Am. Chem. Soc. 2003, 125, 13559. (25) Murray, C. B.; Murray, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 1993, 115, 8706. (26) Motevalli, M.; OBrien, P.; Walsh, J. R.; Watson, I. M. Polyhedron 1996, 15, 2801. (27) OBrien, P.; Otway, D. J.; Walsh, J. R.; Chem. Vap. Depos. 1997, 3, 227. (28) Danek, M.; Jensen, K. F.; Murray, C. B.; Bawendi, M. G. Chem. Mater. 1996, 8, 173. (29) Snyder, R. L.; Fiala, J.; Bunge, H. J. Defect and microstructure analysis by diffraction, Oxford University Press, New York, 1999. (30) Tolbert, S. H.; Alivisatos, A. P. Science 1994, 265, 373. (31) Tolbert, S. H.; Alivisatos, A. P. Annu. Rev. Phys. Chem. 1995, 46, 595. (32) Bailey, R. E.; Nie, S. M. J. Am. Chem. Soc. 2003, 125, 7100. (33) Manna, L.; Scher, E. C.; Li, L. S.; Alivisatos, A. P. J. Am. Chem. Soc. 2002, 124, 7136.
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(34) Peng, X. G.; Manna, L.; Yang, W. D.; Wickham, J.; Scher, E.; Kadavanich, A.; Alivisatos, A. P. Nature 2000, 404, 59.
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Chapter 1 General introduction

In both cases, highly luminescent CdSe nanocrystals are

Chapter 2 Experimental section

Sulfur in dodecylamine was swiftly injected into this solution

Sulfur in dodecylamine was swiftly injected into this solution

2.2.4 Synthesis of CdS nanocrystals using bis(diethyldithiocarbamate)-cadmium(II) compounds as single-source precursor

Cd(S2CNEt2)2 was fully dissolved in tri-n-octylphosphine

2.2.5 Synthesis of ZnS nanocrystals using bis(diethyldithiocarbamate)-zinc(II) compounds as single-source precursor

Zn(S2CNEt2)2 was fully dissolved in tri-n-octylphosphine

2.2.6 Synthesis of ZnxCd1-xS nanocrystals using bis(diethyldithiocarbamate)cadmium(II)/zinc(II) compounds as single-source precursors

Cd(S2CNEt2)2 and Zn(S2CNEt2)2 were both dissolved in tri-n-octylphosphine

Light defracted in phase

nanocrystals possess quantum-confinement wavelength-tunable optical absorption and

nanocrystals at elevated temperature in this synthesis approach, and the rapid

10 sec 2 min 10 min 30 min

10 sec 2 min 10 min 30 min

10 sec 30 sec 2 min 5 min 10 min

10 sec 30 sec 2 min 5 min 10 min

30 sec 2 min 10 min 30 min

30 sec 2 min 10 min 30 min

Figure 3.6 Powder X-ray diffraction pattern of Zn0.17Cd0.83S nanocrystals.

10 sec 2 min 10 min 30 min

10 sec 2 min 10 min 30 min

Figure 3.8 Powder X-ray diffraction pattern of Zn0.23Cd0.77S nanocrystals.

10 sec 30 sec 2 min 10 min 30 min

10 sec 30 sec 2 min 10 min 30 min

10 sec 2 min 10 min 30 min

10 sec 2 min 10 min 30 min

30 sec 2 min 10 min 30 min

30 sec 2 min 10 min 30 min

60 min 30 min 5 min 2 min 1 min 30 sec

ZnS, 4.4 nm Zn0.42Cd0.58S, 4.3 nm

Zn0.28Cd0.72S, 4.2 nm Zn0.23Cd0.77S, 4.3 nm

Zn0.17Cd0.83S, 4.5 nm CdS/Cd(Ac)2, 7.4 nm CdS/Cd(ST)2, 4.1 nm

410 0.0 0.1 0.2 0.3 0.4 0.5 0.6

Molar Composition (% Zn)

Molar Compsotison (% Zn)

4.2.2.2 UV-vis spectroscopy

4.2.2.3 X-ray diffraction

4.2.3 Synthetic methods

Figure 4.1 Schematic representation of the growth of nanocrystals.

10 min 20 min 30 min

10 min 20 min 30 min

Figure 4.3 Powder X-ray diffraction pattern of CdS nanocrystals.

10 min 20 min 30 min

10 min 20 min 30 min

Figure 4.5 Powder X-ray diffraction pattern of ZnS nanocrystals.

10 min 20 min 30 min

10 min 20 min 30 min

002 110 112

Figure 4.7 Powder X-ray diffraction pattern of Zn0.4Cd0.6S nanocrystals.

(a) (c) (b)

Absorbance / PL Intensity (a.u.)

Band edge (446 nm)

Figure 4.12 TEM images of CdS nanocrystals.

Average Dimater = 4.2 nm

25 20 15 10 5 0 3.0 3.5 4.0 4.5 5.0 5.5

Figure 4.14 TEM images of ZnS nanocrystals.

Average Diameter = 5.1 nm

Figure 4.16 TEM images of Zn0.4Cd0.6S nanocrystals.

Average Diameter = 6.1 nm

0 4.8 5.6 6.4 7.2 8.0

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