Rozprawy doktorskie na temat „White light producing materials”

Thesis (M. Eng.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2006.
Includes bibliographical references.
It is well known that the use of high-brightness LEDs for illumination has the potential to substitute conventional lighting and revolutionize the lighting industry over the next 10 to 20 years. However, successful penetration of this extremely large lighting market would require vast improvements in power conversion efficiencies, color index, light output per device and drastic reduction in cost. Quantum Dot white LED (QD WLED) technology may be one of the best choices, due to its higher energy efficiency, larger color render in index, better versatility and more importantly lower cost, compared to conventional blue LED plus YAG: Ce yellow phosphor technology. Due to the fundamental difference of the material structure, QD LEDs will win a steady position among existing white LED patents and a hybrid fabless plus IP business model has the best position to promote this technology to maximize its benefits and potential for the entire LED industry.
by Xinyue Zhao.
M.Eng.

Thesis (M. Eng.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007.
Includes bibliographical references.
The discovery of high brightness (white) light emitting diode (LED) is considered as a real threat to the current lighting industry in various applications. One of the most promising sectors would be using white LED to replace the current Cold Cathode Fluorescent Light (CCFL) technology as the backlight of the large screen Liquid Crystal Display (LCD) screen due to the fact that LCD is a rapidly booming market.
by Chian Myau Soon.
M.Eng.

In this thesis we examine the feasibility of developing a white light source capable of producing colors between 2500 and 7500 Kelvin on the black-body radiator spectrum by simply adjusting amperage to a blue and ultraviolet (UV) light emitting diode (LED). The purpose of a lighting source of this nature is to better replicate daylight inside a building at a given time of day. This study analyzes the proposed light source using a 385 nm UV LED, a 457 nm blue LED, a 479 nm blue LED, a 562 nm peak cerium doped yttrium aluminum garnet (YAG:Ce) phosphor, and a 647 nm peak selenium doped zinc sulfide (ZnS:Se) phosphor. Our approach to this study initially examined optical performance of yellow-emitting phosphor (YAG:Ce) positioned at specific distances above a blue LED using polydimethylsiloxane (PDMS) as a substrate. An understanding of how phosphor concentration within the PDMS, the thickness of the PDMS, and how substrate distance from the LED die affected light intensity and color values (determined quantitatively by utilizing the 1931 CIE 2° Standard Observer) enabled equations to be developed for various lens designs to efficiently produce white light using a 457 nm peak wavelength LED. The combination of two luminescent sources (457 nm LED and YAG:Ce) provided a linear trend on the 1931 CIE diagram which required a red illumination source to obtain Kelvin values from 2500 to 7500. Red-emitting phosphor (ZnS:Se), selected to compliment the system, was dispersed with YAG:Ce throughout PDMS where they were stimulated with a blue LED thereby enabling all desired Kelvin values with differing concentration lenses. Stimulating ZnS:Se with the addition of a UV LED did not provide the ability to change the color value of the set up to the degree required. Many other factors resulted in the decision to remove the UV LED contribution from the multi-Kelvin light source design. The final design incorporated a combination of ZnS:Se and YAG:Ce stimulated with a blue LED to obtain a 2500 Kelvin value. A separate blue LED provides the means to obtain 7500 Kelvin light and the other color values in between, with a linear approximation, by adjusting the amperages of both LEDs. In addition to investigating the feasibility of obtaining the Kelvin values from 2500 to 7500, this thesis also examined the problem of ZnS:Se’s inability to cure in PDMS and a method to create a lens shape to provide equal color values at all points above a phosphor converted LED source. ZnS:Se was found to be curable in PDMS if first coated with a low viscosity silicon oil prior to dispersion within PDMS. The lens configuration consists of phosphors equally distributed in PDMS and cured in the shape of a Gaussian distribution unique to multiple factors in LED-based white light design.

Les matériaux hybrides organiques inorganiques ont attirés l'attention vue qu'ils présentent des propriétés optiques et optoélectroniques fascinantes comme la forte photoluminescence même à température ambiante. Cet axe de recherche relativement nouveau, sur cette famille de matériaux, offre une variété d’opportunités technologiques. Dans ce contexte, nous nous sommes intéressés par l'étude des propriétés optiques des deux matériaux hybrides organiques inorganiques (C6H11NH3)2[PbI4] et (C6H11NH3)2[PbBr4], et principalement leurs propriétés de luminescence. Les résultats montre que sous excitation dans l'ultraviolet, (C6H11NH3)2[PbBr4] émet de la lumière blanche, même à température ambiante, ce qui présente un grand intérêt de l'utilisation de ces matériaux comme source d'émission de la lumière blanche. L'origine de cette émission a été étudié par différentes techniques comme la photoluminescence résolution en temps
Inorganic organic hybrid materials have attracted a great attention do to their special structure and important optical such as the high luminescence, even at room temperature. This relatively new research on this family of materials, offers a variety of technological opportunities. In this context, we are interested in the study of optical properties of both inorganic and organic hybrid materials (C6H11NH3)2[PbI4] and (C6H11NH3)2[PbBr4], and mainly their luminescence properties. The results shows that under ultraviolet excitation, (C6H11NH3)2[PbBr4] show a strong white light emission, even at room temperature, which open a great interest in the use of these materials as a source of the white light emission. The origin of this large emission has been studied by different techniques such as the time resolved photoluminescence measurements

Structural colours arise from the interaction of visible light with nano-structured materials. The occurrence of such structures in nature has been known for over a century, but it is only in the last few decades that the study of natural photonic structures has fully matured due to the advances in imagining techniques and computational modelling. Even though a plethora of different colour-producing architectures in a variety of species has been investigated, a few significant questions are still open: how do these structures develop in living organisms? Does disorder play a functional role in biological photonics? If so, is it possible to say that the optical response of natural disordered photonics has been optimised under evolutionary pressure? And, finally, can we exploit the well-adapted photonic design principles that we observe in Nature to fabricate functional materials with optimised scattering response? In my thesis I try to answer the questions above: I microscopically investigate $\textit{in vivo}$ the growth of a cuticular multilayer, one of the most common colour-producing strategies in nature, in the green beetles $\textit{Gastrophysa viridula}$ showing how the interplay between different materials varies during the various life stages of the beetles; I further investigate two types of disordered photonic structures and their biological role, the random array of spherical air inclusions in the eggshells of the honeyguide $\textit{Prodotiscus regulus}$, a species under unique evolutionary pressure to produce blue eggs, and the anisotropic chitinous network of fibres in the white beetle $\textit{Cyphochilus}$, the whitest low-refractive index material; finally, inspired by these natural designs, I fabricate and study light transport in biocompatible highly-scattering materials.

碩士
長庚大學
光電工程研究所
98
This thesis is divided into two parts. we have fabricated a series of highly efficient white-emitting polymer devices possessing a single emitting layer containing a hole-transporting host polymer, PVK, and electron-transporting auxiliary (OXD7), These doubly doped devices all exhibited an intense white light emission and close to the standard white light region. In the first part, the white emitting polymer device doped with blue-light-emitting iridium phosphor (FIrpic) and red-light-emitting osmium phosphor (Os(fppz)),and electron-transporting layer fabricated by TPBi. The CIE of the first white emitting polymer device is (0.33, 0.35), the maximum luminescence efficiency of 19.8cd/A and the maximum external quantum efficiency of 10.8 % was achieved. In the second part, the white emitting polymer device doped with blue-light-emitting phosphor (FIrpic) and red-light-emitting osmium phosphor (Os(bpftz)), After the modification of electron transporting layer in these WPLEDs, the maximum forward viewing luminescence efficiency of 46.6 cd/A (79.2 cd/A for total viewing) and power efficiency of 29.1 lm/W (49.5 lm/W for total viewing) was achieved, which is comparable to those reported for the state-of-the-art vacuum deposited small molecule WOLEDs.

博士
國立交通大學
應用化學系所
97
This thesis is divided into two parts, part A regarding the synthesis and characterization of two novel host materials for phosphorescent OLEDs; part B regarding the fabrication and character discussion of the highly efficient white polymer light emitting devices. In first section of part A, we report the synthesis and characterization of a novel silane/fluorene hybrid, TPSi-F, used as the host material for blue phosphorescent devices. TPSi-F is constructed by linking both tetraphenylsilane and phenyl substituted fluorene moieties through a non-conjugated, sp3-hybrided carbon atom (C-9) to enhance its thermal and morphological stabilities, while maintaining the much needed, higher singlet and triplet energy gap. Highly efficient sky-blue phosphorescent OLEDs were obtained when employing TPSi-F as the host and FIrpic as the guest, the maximum external quantum efficiency (max. EQE) of this device reached as high as 15 % (30.6 cd/A). Furthermore, upon switching the guest from FIrpic to a new blue phosphor FIrfpy, the saturated-blue OLEDs were realized with the max. EQE being 9.4 % (15.1 cd/A). These TPSi-F based blue phosphorescent devices show a 2-fold enhancement in the device efficiency, comparing with reference devices based on conventional host material mCP. In second section of part A, we report a novel host material TFTPA that contains a triphenylamine core and three 9-phenyl-9-fluorenyl peripheries, was effectively synthesized through a Friedel–Crafts-type substitution reaction. Owing to the presence of its sterically bulky 9-phenyl-9-fluorenyl groups, TFTPA exhibits a high glass transition temperature (186 °C) and is morphologically and electrochemically stable. In addition, as demonstrated from atomic force microscopy measurements, the aggregation of the triplet iridium dopant is significantly diminished in the TFTPA host, resulting in a highly efficient full-color phosphorescence. The performance of TFTPA-based devices is far superior to those of the corresponding mCP- or CBP-based devices, particularly in blue- and red-emitting electrophosphorescent device systems. The efficiency of the FIrpic-based blue-emitting device reached 12% (26 cd/A) and 18 lm/W at a practical brightness of 100 cd/m2; the Ir(piq)2acac-based red-emitting device exhibited an extremely low turn-on voltage (2.6 V) and a threefold enhancement in device efficiency (9.0 lm/W) relative to those of reference devices based on the CBP host material. In part B, we have fabricated a series of highly efficient white emitting polymer devices possessing a single emitting layer containing a hole-transporting host polymer, PVK, and electron-transporting auxiliary (PBD or OXD7), doped with blue-light-emitting dye and red-light-emitting osmium phosphor. These doubly doped devices all exhibited an intense white light emission and close to the standard white light region. After the modified of electron transporting layer in these WPLEDs, the maximum forward viewing luminescence efficiency of 36.1 cd/A (61.4 cd/A for total viewing) and power efficiency of 23.4 lm/W (39.8 lm/W for total viewing) was achieved, which is comparable to those reported for the state-of-the-art vacuum deposited small molecule WOLEDs.

碩士
國立交通大學
電子物理系所
98
This dissertation aims to utilize blade-coating method to fabricate efficient phosphorescent multilayer polymer light-emitting diode (PLED). Iridium complexes are mixed with poly-(vinylcarbazole) (PVK) to form the emissive layer. For yellow phosphorescent PLED, tris[2-(p-tolyl)pyridine]iridium(III) (Ir(mppy)3) and tris[2-(4-n-hexylphenyl)quinoline)]iridium(III) (Hex-Ir(phq)3) are used as green and red dopants respectively. The blending ratio of Ir(mppy)3 and Hex-Ir(phq)3 is 13:1. The efficiency of 23 cd/A and the luminance of 30000cd/m2 are obtained. As for white phosphorescent PLED with single emissive layer, Hex-Ir(phq)3, Ir(mppy)3 and bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III) (FIrpic) are used as dopants in the ratio of 1:0.5:45. The efficiency of 8.1 cd/A and the luminance 6000cd/m2 are achieved. The Commission Internationale de l’Eclairage (CIE) coordinates are stable from 8V to 15 V and only slight changes can be observed from (0.35, 0.42) to (0.36, 0.43). By substituting Hex-Ir(phq)3 with deep red Hex-Ir(piq)3, CIE coordinate (0.35, 0.35) is obtained as the blending ratio Hex-Ir(piq)3 : Ir(mppy)3 : FIrpic = 15:1:480. The light from device uses Hex-Ir(piq)3 is more close to pure white.

碩士
國立清華大學
物理學系
91
The generation of white-light continuum by femtosecond laser pulses in transparent dielectric materials is investigated with 800-nm pump wavelength and self-phase modulation is the main process to produce the physical phenomenon. Our research is focused on the characterizations of white-light spectra width, polarization, pulse width, and frequency chirping with different materials like water, alcohol, methanol, sapphire, quartz, pyrex glass, calcite etc. For white-light polarization, a self-induced change in polarization of the white-light continuum is observed in trigonal crystal structure. For white-light spectra width, we find that the ratio of the medium’s bandgap energy to the photon energy of the incident wavelength determines the amount of spectrum broadening. After the investigation of polarization, the frequency chirp of the white-light continuum is characterized by the Kerr-gate method with 140 fs temporal and 20 nm wavelength resolution. By the investigation of white-light continuum, we can apply to femtosecond time-resolved luminescence spectroscopy, optical pulse compression for generation of ultrashort pulses etc.

碩士
逢甲大學
化學工程學系
104
Polysiloxane based organic-inorganic hybrid (O-I hybrid) encapsulants with high transparency, high refractive index, and thermal resistance were prepared by the sol-gel and UV curing reaction. The chemical structures of the encapsulants were analyzed by Fourier Transform Infrared Spectroscopy (FT-IR) and Si29 NMR. The effects of chemical structure on the refractive index, surface hardness, thermal resistance, and transmittance of encapsulants were investigated through refractometer, nanoindenter, thermogravimetric analysis, and UV/Vis spectrometer. In the second part, graphene was mixed with UV-curable encapsulant to prepare the composite material .The O-I hybrid oligomer encapsulants with and without graphene were mixed with phosphor, and photoinitiator. The mixture was coated on InGaN devices and UV-cured to fabricate white light emitting diodes (WLEDs). The optical, mechanical, and thermal properties of the encapsulants can be tuned by changing their chemical structures. The O-I hybrid materials are encapsulants with high refractive index (n=1.56), good transparency and thermal resistance. After being baked at 150 oC for 48h, the transmittance of encapsulant at 470 nm wavelength decreased from 87% to 86%. Effects of encapsulants on the performance of white light emitting diodes were measured. After continuous lighting, the changes in surface temperature, luminous efficiency, color rendering index, the Commission Internationale de l’Éclairage coordinates, and correlated color temperature (CCT), were investigated to evaluate the stability of the WLED. The WLED surface temperatures of V7g10r1, V7g10r1.5, and V7G4g10r1.5 were 47.5, 46.4, and 44.4℃, respectively. The luminous efficiency, color rendering index, and CCT of V7g10r1 WLED are 130 lm/W(20mA), 84.1, and 4951 K, respectively. After continuous lighting for 20 days, the luminous efficiency, color rendering index, and CCT of V7g10r1 WLED are 113 lm/W(20mA), 82.9, and 4772 K, respectively. For the V7g10r1.5 samples without graphene, the luminous efficiency, color rendering index, and CCT of V7g10r1 WLED are 97.3 lm/W (20mA), 89.8, and 4653 K, respectively. After continuous lighting for 10 days, the luminous efficiency, color rendering index, and CCT of V7g10r1 WLED are 91.5 lm/W (20mA), 86.8, and 3983 K, respectively. For the encapsulants with graphene, the luminous efficiency, color rendering index, and CCT of V7G4g10r1 WLED are 90.1 lm/W (20mA), 89.5, and 4555 K, respectively. After continuous lighting for 10 days, the luminous efficiency, color rendering index, and CCT of V7G4g10r1 WLED are 89.5 lm/W (20mA), 89.2, and 4566 K, respectively. Incorporation of graphene helps to improve the stability of WLED.

White light emitting diodes (LED) have drawn increasing attention due to their low energy consumption, high efficiency and potential to become primary lighting source by replacing conventional light sources. White light emission is usually generated either by coating yellow phosphor on a blue-LED or blending red, green and blue phosphor in an appropriate ratio. Maintaining appropriate proportions of individual components in the blend is difficult and the major demerit of such system is the overall self-absorption, which changes the solution concentration. This results in uncontrolled changes in the whiteness of the emitted light. Zinc Oxide (ZnO), a wide bandgap semiconductor with a large exciton binding energy at room temperature has been recognized as a promising material for ultraviolet LEDs and laser diodes. Tuning of structural, optical and electrical properties of ZnO thin films by different dopants (Lithium, Indium and Gallium) is dealt in this thesis. The achievement of white light emission from a semiconducting material without using phosphors offers an inexpensive fabrication technology, good luminescence, low turn-on voltage and high efficiency. The present work is organized chapter wise, which has 8 chapters including the summary and future work. Chapter 1: Gives a brief discussion on the overview of ZnO as an optoelectronic material, crystal structure of semiconductor ZnO, the effect of doping, optical properties and its possible applications in optoelectronic devices. Chapter 2: Deals with various deposition techniques used in the present study, includes pulsed laser deposition and thermal evaporation. The experimental set up details and the deposition procedures are described in detail. A brief note on the structural characterization equipments, namely X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and the optical characterization techniques namely Raman spectroscopy, transmission spectroscopy and photoluminescence (PL) spectroscopy is presented. The electrical properties of the films were studied by current- voltage, capacitance - voltage and Hall Effect measurements and the experimental details are discussed. Chapter 3: High quality ZnO/Si heterojunctions fabricated by growing ZnO thin films on p-type Si (100) substrate by pulsed laser deposition without using buffer layers are discussed in this chapter. The crystallinity of the heterojunction was analyzed by high resolution X-ray diffraction and atomic force microscopy. The optical quality of the film was analyzed by room temperature (RT) photoluminescence measurements. The high intense band to band emission confirmed the high quality of the ZnO thin films on Si. The electrical properties of the junction were studied by temperature dependent resistivity, current- voltage measurements and RT capacitance-voltage (C-V) analysis. ZnO thin film showed the lowest resistivity of 6.4x10-3 Ω.cm, mobility of 7 cm2/V.sec and charge carrier concentration of 1.58x1019cm-3 at RT. The charge carrier concentration and the barrier height (BH) were calculated to be 9.7x1019cm-3 and 0.6 eV respectively from the C-V plot. The BH and ideality factor, calculated by using the thermionic emission (TE) model were found to be highly temperature dependent. We observed a much lower value in Richardson constant, 5.19x10-7 A/cm2K2 than the theoretical value (32 A/cm2K2) for ZnO. This analysis revealed the existence of a Gaussian distribution (GD) with a standard deviation of σ2=0.035 V. By implementing GD to the TE, the values of BH and Richardson constant were obtained as 1.3 eV and 39.97 A/cm2K2 respectively from the modified Richardson plot. The obtained Richardson constant value is close to the theoretical value for n-ZnO. These high quality heterojunctions can be used for solar cell applications. Chapter 4: This chapter describes the structural and optical properties of Li doped ZnO thin films and the properties of ZnO/Li doped ZnO multilayered thin film structures. Thin films of ZnO, Li doped ZnO (ZLO) and multilayer of ZnO and ZLO (ZnO/ZLO) were grown on silicon and Corning glass substrates by pulsed laser deposition technique. Single phase formation and the crystalline qualities of the films were analyzed by X-ray diffraction and Li composition in the film was investigated to be 15 Wt % by X-ray photoelectron spectroscopy. Raman spectrum reveals the hexagonal wurtzite structure of ZnO, ZLO and ZnO/ZLO multilayer, confirms the single phase formation. Films grown on Corning glass show more than 80 % transmittance in the visible region and the optical band gaps were calculated to be 3.245, 3.26 and 3.22 eV for ZnO, ZLO and ZnO/ZLO respectively. An efficient blue emission was observed in all films that were grown on silicon (100) substrate by photoluminescence (PL). PL measurements at different temperatures reveal that the PL emission intensity of ZnO/ZLO multilayer was weakly dependent on temperature as compared to the single layers of ZnO and ZLO and the wavelength of emission was independent of temperature. Our results indicate that ZnO/ZLO multilayer can be used for the fabrication of blue light emitting diodes. Chapter 5: This chapter is divided in to two parts. The fabrication and characterization of In doped ZnO thin films grown on Corning glass substrate is discussed in the first section. Zinc Oxide (ZnO) and indium doped ZnO (IZO) thin films with different indium compositions were grown by pulsed laser deposition technique. The effect of indium concentration on the structural, morphological, optical and electrical properties of the film was studied. The films were oriented along the c-direction with wurtzite structure and are highly transparent with an average transmittance of more than 80 % in the visible wavelength region. The energy band gap was found to be decreasing with increasing indium concentration. High transparency makes the films useful as optical windows while the high band gap values support the idea that the film could be a good candidate for optoelectronic devices. The value of resistivity observed to be decreasing initially with doping concentration and subsequently increasing. The XPS and Raman spectrum confirm the presence of indium in indium doped ZnO thin films. The photoluminescence spectrum showed a tunable red light emission with different In concentrations. Undoped and In doped ZnO (IZO) thin films were grown on Pt coated silicon substrates (Pt/Si) to fabricate Pt/ZnO:Inx Schottky contacts (SC) is discussed in the second section. The SCs were investigated by conventional two probe current-voltage (I-V) measurement and by the I-V spectroscopy of conductive atomic force microscopy (C-AFM). X-ray diffraction technique was used to examine the thin film quality. Changes in various parameters like Schottky barrier height (SBH) and ideality factor (IF) as a function of temperature were presented. The estimated BH was found to be increasing and the IF was found to be decreasing with increase in temperature. The variation of SBH and IF with temperature has been explained by considering the lateral inhomogeneities in nanometer scale lengths at metal–semiconductor (MS) interface. The inhomogeneities of SBH in nanometer scale length were confirmed by C-AFM. The SBH and IF estimated from I-V spectroscopy of C-AFM showed large deviation from the conventional two probe I-V measurements. IZO thin films showed a decrease in SBH, lower turn on voltage and an enhancement in forward current with increase in In concentration. Chapter 6: In this chapter the properties of Ga doped ZnO thin films with different Ga concentrations along with undoped ZnO as a reference is discussed. Undoped and Ga doped ZnO thin films with different Ga concentrations were grown on Corning glass substrates by PLD. The structural, optical and electrical properties of Ga doped ZnO thin films are discussed. The XRD, XPS and Raman spectrum reveal the phase formation and successful doping of Ga on ZnO. All the films show good transmittance in the visible region and the photoluminescence of Ga doped ZnO showed a stable emission in the blue- green region. The resistivity of Ga doped ZnO thin films was found to be first decreasing and then increasing with increase in Ga concentrations. Chapter 7: The effect of co-doping to ZnO on the structural, optical and electrical properties was described in this chapter. Ga and In co-doped ZnO (GIZO) thin films together with ZnO, In doped ZnO (IZO), Ga doped ZnO (GZO), IZO/GZO multilayer for comparison, were grown on Corning glass and boron doped Si substrates by PLD. GIZO showed better structural, optical and electrical properties compared with other thin films. The Photoluminescence spectra of GIZO showed a strong white light emission and the current-voltage characteristics showed relatively lower turn on voltage and larger forward current. The CIE co-ordinates for GIZO were observed to be (0.31, 0.33) with a CCT of 6650 K, indicating a cool white light and established a possibility of white light emitting diodes. Finally the chapter 8 presents the summary derived out of the work and a few suggestions on future work.

碩士
國立中正大學
光機電整合工程所
93
Organic light emitting devices were deposited on Indium tin oxide (ITO) substrate by high vacuum evaporator system. In our study, the device configurations of white organic light emitting diodes (WOLEDs) using multilayer structure were ITO/NPB /Host：Firpic：Ir(DBQ)2(acac) /TPBI /Mg:Ag. Three different host materials, including mCP, TCTA, and CBP, are individually used in the emitting layer to fabricate the devices. Effects of different host materials on the photoelectronic characteristics of white-light organic light-emitting diodes have been systematically investigated. It is proved that with the use of suitable high energy-gap host materials, the brightness of WOLEDs can be significantly improved. Evidence showed that the use of the high energy-gap materials make the energy transfer between the host and guest materials easier. Hence, the brightness of OLED can be further enhanced. In this study, the energy is transferred from the high energy-gap host material to the guest materials Firpic and Ir(DBQ)2(acac), and then the blue and red light is produced by the Firpic and Ir(DBQ)2(acac), respectively. By the mixture of the red and blue light, the white light emission is achieved.

abstract: White organic light emitting diodes (WOLEDs) are currently being developed as the next generation of solid state lighting sources. Although, there has been considerable improvements in device efficiency from the early days up until now, there are still major drawbacks for the implementation of WOLEDs to commercial markets. These drawbacks include short lifetimes associated with highly efficient and easier to fabricate device structures. Platinum (II) complexes are been explored as emitters for single emissive layer WOLEDs, due to their higher efficiencies and stability in device configurations. These properties have been attributed to their square planar nature. Tetradentate platinum (II) complexes in particular have been shown to be more rigid and thus more stable than their other multidentate counterparts. This thesis aims to explore the different pathways via molecular design of tetradentate platinum II complexes and in particular the percipient engineering of a highly efficient and stable device structure. Previous works have been able to obtain either highly efficient devices or stable devices in different device configurations. In this work, we demonstrate a device structure employing Pt2O2 as the emitter using mCBP as a host with EQE of above 20% and lifetime values (LT80) exceeding 6000hours at practical luminance of 100cd/m2. These results open up the pathway towards the commercialization of white organic light emitting diodes as a solid state lighting source.
Dissertation/Thesis
Masters Thesis Materials Science and Engineering 2016

The International Energy Agency estimated that lighting accounts for ~19% of the total worldwide energy consumption. Light emitting diodes (LEDs) have higher efficiency compared to that of conventional lighting sources. The commercial white-LEDs (WLEDs) are based on broad-band Y3Al5O12:Ce3+ (YAG:Ce) yellow phosphor in combination with blue LED chips through a low cost and simple procedure, in which the YAG:Ce phosphor is directly packed on the blue InGaN chip. However, such two colour-based WLEDs exhibit poor colour rendering index (CRI, usually <75), high correlated colour temperature (CCT, >6500 K), and chromaticity drifts, which cannot fully satisfy the applications of lighting and backlighting of the displays. Also, LEDs still face some other drawbacks such as the relatively low efficient green emission, termed the ³green gap´ issXe. A promising alternative strategy is based on the downshift of the electroluminescence of near ultra-violet (NUV)/blue LEDs into the green spectral region by UV/blue-down shifting phosphors. Thus, novel efficient white and green-emitting materials for the phosphor-converted LED applications are required. In this thesis, organic-inorganic hybrids (ureasils, d-U(600)) doped with green emitting Tb3+-based complexes were applied in combination with NUV-LED chips to fabricate efficient green LED prototypes. To improve CRI and CCT of commercial WLEDs, novel blue-light excited La2Ce2O7:Eu3+ red phosphors were also successfully synthesised and characterized. Moreover, tuned white light emitters involving d-U(600) hybrids doped with lanthanide (Ln3+=Tb3+, Eu3+)-based complexes, fluorescent dyes (e.g. coumarin), and carbon dots were also prepared and optically characterised revealing intriguing CCT, CRI and photostability towards novel WLEDs.
A Agência Internacional de Energia estimou que o sector de iluminação representa cerca de 19% do consumo total de energia mundial. Os díodos emissores de luz (LEDs) têm maior eficiência em comparação com as fontes de iluminação convencionais. Os LEDs brancos comerciais (WLEDs) são baseados na combinação de LEDs azuis baseados em InGaN com o luminóforo Y3Al5O12:Ce3+ (YAG:Ce). Este material, que é um emissor de banda larga na região espectral do amarelo. é depositado de forma simples e a baixo custo sobre o LED azul. No entanto, a emissão deste WLEDs baseia-se na adição de duas cores tendo um índice de reprodução de cor baixo (CRI, geralmente <75), elevada temperatura de cor (CCT, > 6500 K) e variação de cromaticidade, que são claras desvantagens em aplicações de iluminação e retroiluminação. Para além destas desvantagens, estes LEDs ainda apresentam emissão na região do verde relativamente menos eficiente (usualmente designado em linguagem inglesa como ³green gap issue´). Uma estratégia alternativa a estes LEDs baseia-se na utilização de dispositivos emissores nas regiões espectrais do ultravioleta próximo (NUV) e do azul combinados com um material capaz de desviar esta emissão para a região do visível. Assim, novos materiais emissores eficientes quer de luz verde quer de luz branca para as aplicações em LEDs são necessários. Nesta tese, híbridos orgânicos-inorgânicos (ureasils, d-U(600)) dopados com complexos à base de Tb3+ emissores no verde foram combinados com NUV-LED comerciais para fabricar protótipos de LED verdes eficientes. Para melhorar o CRI e CCT dos WLEDs comerciais, novos luminóforos de La2Ce2O7:Eu3+ com emissão no vermelho e excitados com LEDs azuis foram, também, sintetizados e caracterizados. Na parte final da tese discute-se a contribuição de novos materiais emissores de luz branca sintonizável baseados em híbridos d-U(600) dopados com complexos de iões lantanídeos (Ln3+=Tb3+, Eu3+), corantes fluorescentes e pontos de carbono com propriedades óticas (CCT, CRI e fotoestabilidade) melhoradas, face ao estado da arte.
Programa Doutoral em Ciência e Engenharia de Materiais

Carbon nanoparticles (CNPs) have drawn great attention in the last few years owing to their unique properties such as excellent water solubility, chemical stability, inertness, low toxicity, good bio-compatibility, and tunable photo physical properties. Recently, researchers have focused on hetero atom (N, S and B) doped CNPs due to their excellent properties. These properties make the CNPs and doped CNPs as potential candidates for a wide range of applications. For example, metal ion detection in aqueous solution, bio-imaging, bio-sensing, photovoltaic devices, cleavage of deoxyribonucleic acid (DNA), and catalysis. Therefore, CNPs are alternative to inorganic semiconductor nanoparticles. However, CNPs with diameter less than 10 nm have been prepared using various approaches including top down and bottom methods. Cutting the bulk carbon from high dimensional to zero dimensional by using either physical or chemical process are classified as top down method. Bottom up method refers the conversion of organic precursor to nano-carbon by using thermal pyrolysis, microwave based hydrothermal method, cage opening of C60 molecules. In the present work, I have dealt with the facile synthesis of CNPs and different hetero atom doped carbon nanoparticles (N-CNPs, B-CNPs, and BN-CNPs) using the hydrothermal method. Based on their intriguing physical and chemical properties, these CNPs/doped-CNPs have been explored for various applications such as (i) metal-free catalysts, (ii) color tunability from red to blue and bio-imaging, (iii) ammonia sensing, (iv) white light generation, and (v) detection of picric acid (PA) in aqueous solution. Finally, I have presented 3D nanodendrites of N-CNPs and Pd NPs and their excellent catalytic mass activity for methanol electro-oxidation and ultra-fast reduction of 4-nitrophenol.

Luminescent materials find numerous applications in recent times and have enriched human lives in several different ways. From display and lighting technologies to security, sensing and biological investigations, luminescent organic compounds have become indispensible and often preferred over their inorganic counterparts. The versatility of organic materials arises from their comparative low costs, ease of fine-tuning, low toxicity and the possibility to develop flexible devices. Even until very recent times, the investigations and usage of organic luminescent materials were mostly limited to solution-state properties. However, with progress of available characterisation techniques and parallel development of their usage in solid-state devices and other applications (e.g. security, forensics, sensing etc.), significantly greater attention has been paid to the development and investigations of solid-state emissive organic materials. In solid-state applications, apart from the molecular properties of any given material, their cumulative i.e. bulk physical properties are of even greater importance. Thus, investigations of structure-property relationships in organic luminescent compounds to understand their molecular and bulk properties are of fundamental interest. In this thesis, NPI (1,8-naphthalimide) and BODIPY (boron-dipyrromethene) dyes were investigated to provide a broad overview of their structure-property correlations. Among commonly encountered organic luminescent materials, NPIs and BODIPYs have emerged as two broad classes of luminescent organic compounds, finding applications as functional luminescent materials in various fields. However, lack of understanding for controlling the cumulative emissive properties of these compounds has limited their usage as active solid-state emitters in various applications. This thesis presents several new insights into the molecular and bulk emissive properties of these two classes of luminescent dyes (NPIs and BODIPYs). The contents of the six chapters contained in this thesis are summarised below. Chapter 1 summarises the available understanding of the basic concepts of photoluminescence and the design strategies to develop solid-state luminescent and AIE (aggregation-induced emission) active materials. This chapter also emphasises in the basic nature of the NPI and BODIPY compounds, their substitution patterns and their inherent characteristics and touches upon the relatively unexplored properties of NPI and BODIPY based materials. The importance and scope of the work reported in the thesis is outlined at the end of the chapter. Chapter 2 describes a detailed investigation of a series of seven (4-oxoaryl substituted) NPI compounds (1-7) providing an insight into the molecular and cumulative photophysical behaviour of these compounds. The low ICT characteristics of the NPIs, coupled with the twisted geometry, facilitated solid-state luminescence in these materials. The solution and solid-state luminescent properties of these compounds can be directly correlated to their structural rigidity, nature of substituents and solid-state intermolecular interactions (e.g. π-π stacking, C-H•••O interactions etc.). The solid-state crystal structures of the NPI siblings are profoundly affected by the pendant substituents. All of the NPIs (1-7) show antiparallel dimeric π-π stacking interactions in the solid-state which can further extend in parallel, alternate, orthogonal or lateral fashion depending on the steric and electronic nature of the C-4′ substituents. Structural investigations including Hirsfeld surface analysis methods reveal that while strongly interacting systems show weak to moderate emission in their condensed states, weakly interacting systems show strong emission yields under the same conditions. The nature of packing and extended structures also affects the emission colors of the NPIs in the solid-state. DFT computational studies were utilized to understand the molecular and cumulative electronic behavior of the NPIs. Apart from the investigation of solid-state luminescence, other functional potentials of these NPIs were also explored. One of the compounds (i.e. 4) shows chemodosimetric response towards aqueous Hg(II) species with a ‘turn-on’ response. Also, depending on the molecular flexibility of the compounds, promising AIEE (aggregation-induced emission enhancement) features were observed in these NPIs. Later (in Chapter 3), we developed a systematic investigation in a series of purely organic NPIs, restricting various parameters, to attain a thorough understanding of such AIEE properties. Chapter 3 describes a detailed experimental and computational study in order gain an insight into the AIE (aggregation-induced emission) and AIEE mechanisms in NPI compounds. Systematic structural perturbation was used to fine tune the luminescence properties of three new 1,8-naphthalimides (8-10) in solution and as aggregates. The NPIs (8-10) show blue emission in solution state and the fluorescence quantum yields depend on their molecular rigidity. In concentrated solutions of the NPIs, intermolecular interactions were found to result in quenching of fluorescence. In contrast, upon aggregation (in THF:H2O mixtures), two of the NPIs show aggregation-induced-emission-enhancement (AIEE). The NPIs also show moderately high solid-state emission quantum yields (~10-12.7 %). The AIEE behaviors of the NPIs depend on their molecular rigidity and nature of intermolecular interactions. The NPIs (8-10) show different extents of intermolecular (π-π and C-H•••O) interactions in their solid-state structures depending on their substituents. Detailed photophysical, computational and structural investigations suggest that only an optimal balance of structural flexibility and intermolecular communication is the effective recipe for achieving AIEE characteristics in these NPIs. Chapter 4 presents the design, synthesis and detailed investigations and potential applications of a series of NPI-BODIPY dyads (11-13). The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges and the compounds only differ structurally with respect to methyl substitutions on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in these molecular dyads (11- 13). Dyads 11-13 show dual emission in solution state originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibility of the systems. The dyads also show significant AIES (Aggregation-Induced-Emission Switching) features upon formation of nano-aggregates in THF-H2O mixtures with visual changes in emission from green to red color. Whereas the flexible and aggregation prone system (i.e. compound 11) shows aggregation-induced enhancement of emission, rigid systems with less favorable intermolecular interactions (i.e. compound 12-13) show aggregation-induced quenching of emission. The emission-intensity vs. the structural-flexibility correlations were found to be reverse in solution and aggregated states. Photophysical and structural investigations suggest that the intermolecular interactions (e.g. π-π stacking etc.) play major role in controlling emission of these compounds in aggregated states. Similar trends were also observed in the solid-state luminescence of these compounds. The applications of the luminescent dyads 11-13 as live-cell imaging dyes was also investigated. Chapter 5 describes investigations of photophysical properties of a series of six BODIPY dyes (14-19) in which there is a systematic alteration of a common -C6H4Si(CH3)3 substituent. Inrelated constitutional isomers, the systematic increment of steric congestion and lowering of molecular symmetry around the BODIPY core result in a steady increment of solution and solid- state fluorescence quantum yields. The increasing fluorescence quantum yields (solution, solid state) with increasing steric congestions show that the molecular free rotation and aggregation-induced fluorescence quenching of BODIPYs can be successfully suppressed by lowering the flexibility of the molecules. Photophysical and DFT investigations reveal that the electronic band gap in any set of these constitutional isomers remain almost similar. However, the crystal structures of the compounds reveal that the solid-state colour and quantum yields of the compounds in solid-state are also related to the nature of intermolecular interactions. Chapter 6 demonstrates the use of DFT computational methods to understand the effect of alkyl groups in governing the basic structural and electronic aspects of BODIPY dyes. As demonstrated in Chapter 4 and Chapter 5, apparently electronically inactive alkyl groups can be of immense importance to control the overall photophysics of BODIPYs. In this context, a systematic strategy su was utilized considering all possible outcomes of constitutionally-isomeric molecules to understand the effects of alkyl groups on the BODIPY molecules. Four different computational methods were employed to ascertain the unanimity of the observed trends associated with the molecular properties. In line with experimental observations, it was found that alkyl substituents in BODIPY dyes situated at 3/5-positions effectively participate in stabilization as well as planarization of such molecules. Screening of all the possible isomeric molecular systems was used to understand the individual properties and overall effects of the typical alkyl substituents in controlling several basic properties of such BODIPY molecules.