Doping And photophysical Properties Of II-VI Semiconductor Nanocrystals
Semiconductor nanocrystals with sizes comparable to the corresponding bulk excitonic diameter exhibit unique size-dependent electronic and optical properties resulting from quantum confinement effect. Such nanocrystals not only allow the study of evolution of bulk properties from the molecular limit providing important fundamental understandings, but also have great technological implications, leading to intense research over the past several years. Besides tuning the crystal size in the nm regime to obtain novel properties, an additional route to derive new functionalities has been to dope transition metal ions into a semiconductor host. Thus, transition metal doped nanocrystals are of great interest since it allows two independent ways to functionalize semiconductor materials, one via the tunability of properties by size variation and other due to properties of such dopants. Chapter 1 of the thesis provide a general introduction to the subject matters dealt in with this thesis, while the necessary methodologies have been discussed in chapter 2. Chapters 3 and 4 of this thesis deal with nanocrystal doping. Following suggestions in previous literatures that the doping of nanocrystal depends strongly upon the crystal structure of the synthesized host nanocrystal, we have studied the phase-transformation between the somewhat zinc-blende and the usual wurtzite structures for CdS and CdSe nanocrystals in chapter 5. In chapter 6 we have pointed out that a gradient structure is essential to achieve nearly ideal photoluminescence efficiency using heterostructured nanocrystals and also achieved strong two-photon absorptions, adding optical bifunctionality to these nanocrystals. Finally, in chapter 7, we establish different approaches to generate white-light using nanocrystals and their unique advantages, as a first step to realizing white light emitting devices. Chapter 1 provides a brief introduction to various interesting properties and concepts relevant for the studies carried out in the subsequent chapters of this thesis. The present status of the research in the field of semiconductor nanocrystals with an emphasis on synthesizing high quality nanocrystals, doping of nanocrystals and exciting optical properties exhibited by these nanocrystals has been discussed. We have discussed the existing theories and practices of colloidal synthesis that allow us to prepare high quality semiconductor nanocrystals with required size and very narrow size distribution. Optical properties, covering excitonic fine structure, photoluminescence, auger recombination and two-photon absorption have been discussed. We have described heterostructured nanocrystals of different types, particularly in the light of enhancing photoluminescence quantum yield. The difficulty in doping Mn2+ ion in semiconductor nanocrystals and the recent developments in this field have been addressed. Chapter 2 describes experimental and theoretical methodologies that have been employed to study different nanocrystal systems reported in this thesis. The topics covered in this chapter include UV-visible absorption spectroscopy, steady-state and time-resolved luminescence spectroscopy, X-ray diffraction, transmission electron microscopy, electron spin resonance spectroscopy, photoemission spectroscopy, two-photon absorption and least-squared-error fitting. Chapter 3 presents a detailed study of water soluble Mn2+-doped CdS nanocrystals synthesized using colloidal routes. Earlier efforts to dope Mn2+ ion into CdS nanocrystals and therefore, obtain the characteristic orange emission, have been largely impeded by the strong overlap of surface state emission of the host and Mn2+ d-emission. We are the first ones to obtain a distinct Mn2+ d-related emission at around 620 nm, well-separated from the surface state emission with its maximum near 508 nm. In spite of using very high (~30%) concentration of Mn2+ precursor, only ~1% Mn2+ was found in the final product, which is consistent with previous literatures, where Mn2+ doping in such nanocrystals was found to be extremely difficult. Most interestingly, present results establish that Mn2+ ion is found to be incorporated preferentially in the relatively larger sized nanocrystals compared to the smaller sized ones even within the narrow size distribution achieved for a specific reaction condition. We found that 55 oC is the optimum reaction temperature to synthesize Mn2+-doped CdS nanocrystals, at higher reaction temperatures, Mn2+ ions get annealed out of the substitutional sites, leading to a lower level of doping in spite of the formation of larger sized particles. Additionally, we could tune the color of the Mn2+ d- emission from red (620 nm) to yellow (580 nm) by increasing the reaction temperature from 55 oC to 130 oC. Another important aspect is that the synthesized nanocrystals readily dissolve in water without any perceptible effect on the Mn2+ d emission intensity. Chapter 4 discusses the outstanding problem that a semiconductor host in the bulk form can be doped to a large extent, while the same host in the nanocrystal form resist any appreciable level of doping. We first describe two independent models available in literatures to explain this baffling phenomenon. In one, it was suggested that the doping of Mn2+ ion in such nanoclusters is invariably an energetically unfavorable state, thus, Mn2+ ions get annealed out from the host nanocrystal and an increase in reaction temperature facilitate such annealing, a phenomenon known as self-purification. In the second model, it was suggested that the ease of initial adsorption of Mn2+ ions on specific surfaces of a growing nanocrystal, kinetically controls the extent of impurity doping. Specifically, it is easier to dope zinc-blende nanocrystals compared to their wurtzite counterpart. In contrast, the main claim of this chapter is neither crystal structure nor self-purification is as important in nanocrystal doping as lattice mismatch between the dopant and host lattice. To support this claim, we have doped Mn2+ ions into alloyed ZnxCd1-xS nanocrystals. Ionic radius of Mn2+ ion being in between those of Zn2+ and Cd2+ ions, the lattice mismatch between the host ZnxCd1-xS nanocrystal and MnS could be tuned in either side by tuning the composition “x”. It was gratifying to observe that there is an evident maximum of manganese content for Zn0.49Cd0.51S host nanocrystals that has no lattice mismatch with MnS, and the manganese content decreases systematically with increasing compressive as well as tensile lattice mismatches. Based on lattice parameter tuning, we could dope an extraordinarily higher amount of ~7.5% manganese for x = 0.49, at a reaction temperature as high as 310 oC and in a nanocrystal that exhibit wurtzite structure, which was previously suggested unfavorable for doping. These results prove our hypothesis that the strain fields generated because of the lattice mismatch between the dopant and host, are necessarily long range, much longer than typical nanocrystal dimensions and it tends to relieve itself by ejecting the dopant to the surface of nanocrystals, thus, resisting doping in such nanocrystals. High temperature synthesis, on the other hand, leads to a very high photoluminescence efficiency of ~25%. Chapter 5 deals with the phase-control of CdS and CdSe nanocrystals synthesized employing colloidal routes. CdS nanocrystals exhibit a very sensitive phase transformation from zinc-blende to wurtzite structure by increasing the reaction temperature from 280 to 310 oC, which is also accompanied by an increase in particle size from 6 to 6.8 nm, respectively. More importantly, just by changing the S precursor, it has been possible to change the crystal structure of the CdS nanocrystals at a given synthesis temperature of 310 oC. En route, we have synthesized >12 nm zinc-blende CdS nanocrystal, which is the largest one known in literature and that too employing the highest (310 oC) reaction temperature. Thus, our results contradict with the suggestions already in literatures that low reaction temperature and small crystal size favors zinc-blende structure. Also, we could tune crystal structure between zincblende and wurtzite at a given pressure of the reaction vessel and for a given solvent, just by changing the S-precursor, which is again in contradiction to previously made suggestions in literatures that high pressure or noncoordinating solvents favors the formation of zinc-blende nanocrystals. Instead, we believe that the surface energy might be crucial in stabilizing the usually rare zinc-blende structure for such nanocrystals. Chapter 6 is divided into two sections and deals with optically active heterostructured nanocrystals exhibiting high photoluminescence efficiency and strong two-photon absorption. In section-I, we probe the internal structure of extraordinarily luminescent (quantum yield = 85%) CdSeS nanocrystals making a somewhat unconventional use of Photoelectron spectroscopy, using the tunability of the photon energy from the third generation synchrotron radiation source as well as the traditional Mg Kα and Al Kα photon sources. CdSeS nanocrystals synthesized with Se:S precursor ratios 1:5 and 1:50, emitting red and green light have CdSe/CdSeS/CdS core/gradient-shell/shell and CdSeS/CdS gradient-core/shell structure, respectively. Gradient interface/core tunes the lattice parameters continuously between that of CdSe and CdS minimizing the interface related defects which in turn increases the photoluminescence efficiency even beyond that obtained from traditional core/shell nanocrystals, as evidenced by the nearly single exponential photoluminescence decay dynamics exhibited by these nanocrystals. Quantum mechanical calculations further show that a graded-core/shell structure leads to a remarkable spatial collapse and consequently a stronger overlap of the HOMO and LUMO wavefunctions towards the core region and thereby, making these luminescent beyond the traditional core/shell limit. In section-II, we have synthesized hetero-structured nanocrystals with CdSe rich core and CdS-ZnS hybrid shell using a simple single-step reaction. These nanocrystals exhibit a very rare example of an optically bi-functional material, simultaneously exhibiting high (~65%) photoluminescence efficiency and strong two-photon absorption cross-section of 1923 GM. Open-aperture z-scan technique was used to measure two-photon absorptions. Chapter 7 is divided into two sections and deals with the generation of white-light emitting nanophosphors. Section-I addresses the white-light emission from a blend of blue, green and red emitting CdSeS nanocrystals. Different shades of the emitted white-light were achieved by tailoring the composition of the blende. Chromaticity of the emitted light of a particular blend is independent of excitation wavelength. Section-II discusses a new approach to generate white-light by combining surface-state emission of nanocrystalline host and d-electron transitions from dopant centres, with an example of Mn2+-doped CdS nanocrystals. Relative contributions from both surface-state emission and Mn2+ d-emission can be tuned by controlling the dopant concentration to generate white lights of different shades. Similar to section-I, here again the chromaticity of the emitted light is independent of the excitation wavelength; but this approach offers additional advantages. Since the surface state emission as well as the Mn2+ d-emission are relatively less sensitive to a size variation compared to the band-edge emission, the chromaticity of the emitted light is not critically dependent on the particle size. Most importantly, these nanocrystals exhibit a huge stokes shift between the absorption and emission spectra resulting in a complete absence of the well-known self-absorption problem, thus, chromaticity of the white-light emitted by these nanocrystals remains unchanged both in dilute dispersion form as well as in solid state. Also there are two appendices in the thesis. Appendix A discusses the preparation of InP nanocrystals using a novel solvothermal route. Appendix B contains the equations explaining photoemission intensity ratios between Se and S (ISe/IS) for a model nanocrystal with a given internal structure.
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