Tailoring Plasmonic Enhanced Upconversion in Single NaYF4:Yb3+/Er3+ Nanocrystals

NASA Astrophysics Data System (ADS)

Wang, Ya-Lan; Mohammadi Estakhri, Nasim; Johnson, Amber; Li, Hai-Yang; Xu, Li-Xiang; Zhang, Zhenyu; Alù, Andrea; Wang, Qu-Quan; Shih, Chih-Kang (Ken)

2015-05-01

By using silver nanoplatelets with a widely tunable localized surface plasmon resonance (LSPR), and their corresponding local field enhancement, here we show large manipulation of plasmonic enhanced upconversion in NaYF4:Yb3+/Er3+ nanocrystals at the single particle level. In particular, we show that when the plasmonic resonance of silver nanolplatelets is tuned to 656 nm, matching the emission wavelength, an upconversion enhancement factor ~5 is obtained. However, when the plasmonic resonance is tuned to 980 nm, matching the nanocrystal absorption wavelength, we achieve an enhancement factor of ~22 folds. The precise geometric arrangement between fluorescent nanoparticles and silver nanoplatelets allows us to make, for the first time, a comparative analysis between experimental results and numerical simulations, yielding a quantitative agreement at the single particle level. Such a comparison lays the foundations for a rational design of hybrid metal-fluorescent nanocrystals to harness the upconversion enhancement for biosensing and light harvesting applications.

Intense 2.7 μm mid-infrared emission of Er{sup 3+} in oxyfluoride glass ceramic containing NaYF{sub 4} nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yin; Liu, Xueyun; Wang, Weichao

2016-04-15

Highlights: • Transparent oxyfluoride glass-ceramics containing NaYF{sub 4}:Er{sup 3+} nanocrystals have been prepared. • Intense 2.7 μm emission of the glass-ceramics has been demonstrated. • Prolonged decay lifetimes of Er{sup 3+}:{sup 4}I{sub 11/2} and {sup 4}I{sub 13/2} levels have been achieved. - Abstract: Transparent oxyfluoride glass ceramics containing NaYF{sub 4}:Er{sup 3+} nanocrystals have been prepared by melt quenching and subsequent thermal treatment. X-ray diffraction and high-resolution transmission electron microscopy analysis confirmed the precipitation of NaYF{sub 4} nanocrystals in glass. Energy dispersive spectrometer results evidenced the preferential concentration of Er{sup 3+} ions in nanocrystals. Mid-infrared, upconversion, and near-infrared emissions were measuredmore » upon excitation with 980 nm laser diode and the luminescence mechanisms were discussed. Intense 2.7 μm emission originating from the Er{sup 3+}:{sup 4}I{sub 11/2} → {sup 4}I{sub 13/2} transition was achieved due to the incorporation of Er{sup 3+} ions into the precipitated low phonon energy fluoride nanocrystals. The results indicate that oxyfluoride glass ceramic containing NaYF{sub 4}:Er{sup 3+} nanocrystals is a promising candidate material for 2.7 μm laser.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1,2,3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate thatmore » colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1, 2, 3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. Wemore » demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.; Jean, Joel; Geva, Nadav; Welborn, Matthew; van Voorhis, Troy; Bulović, Vladimir; Bawendi, Moungi G.; Baldo, Marc A.

2016-01-01

Optical upconversion via sensitized triplet-triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.

CdSe/AsS core-shell quantum dots: preparation and two-photon fluorescence.

PubMed

Wang, Junzhong; Lin, Ming; Yan, Yongli; Wang, Zhe; Ho, Paul C; Loh, Kian Ping

2009-08-19

Arsenic(II) sulfide (AsS)-coated CdSe core-shell nanocrystals can be prepared by a cluster-complex deposition approach under mild conditions. At 60 degrees C, growth of an AsS shell onto a CdSe nanocrystal can be realized through the crystallization of a cluster complex of AsS/butylamine in a mixed solvent of isopropanol/chloroform. The new, type I core-shell nanocrystal exhibits markedly enhanced one-photon fluorescence as well two-photon upconversion fluorescence. The nanocrystals can be used for infrared-excited upconversion cellular labeling.

Sub-10 nm lanthanide doped BaLuF{sub 5} nanocrystals: Shape controllable synthesis, tunable multicolor emission and enhanced near-infrared upconversion luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Ling; Lu, Wei; Wang, Haibo

2015-04-15

Highlights: • Sub-10 nm cubic phase BaLuF{sub 5} nanocrystals were synthesized by a hydrothermal method for the first time. • Tunable multicolor from yellow to yellow-green was achieved by controlling Gd{sup 3+} content in BaLuF{sub 5}:Yb/Er system. • Intense near-infrared upconversion luminescence in BaLuF{sub 5}:Gd/Yb/Tm nanocrystal. • The enhancement near-infrared luminescence can be realized by adjusting the content of Gd{sup 3+} in BaLuF{sub 5}:Gd/Yb/Tm system. - Abstract: In this study, sub-10 nm BaLuF{sub 5} nanocrystals with cubic phase structure were synthesized by a solvothermal method using oleic acid as the stabilizing agent. The as-prepared BaLuF{sub 5} nanocrystals were characterized bymore » transmission electron microscopy (TEM), X-ray diffraction (XRD), and analyzed by the upconversion (UC) spectra. The TEM results reveal that these samples present high uniformity. Compared with Gd-free samples, the size of BaLuF{sub 5}:Yb/Er doped with 10% Gd{sup 3+} decreased to 5.6 nm. In addition, BaLuF{sub 5}:Yb/Tm/Gd upconversion nanoparticles (UCNPs) presented efficient near-infrared (NIR)-NIR UC luminescence. Therefore, it is expected that these ultra-small BaLuF{sub 5} nanocrystals with well-controlled shape, size, and UC emission have potential applications in biomedical imaging fields.« less

Using lead chalcogenide nanocrystals as spin mixers: a perspective on near-infrared-to-visible upconversion.

PubMed

Nienhaus, Lea; Wu, Mengfei; Bulović, Vladimir; Baldo, Marc A; Bawendi, Moungi G

2018-03-01

The process of upconversion leads to emission of photons higher in energy than the incident photons. Near-infrared-to-visible upconversion, in particular, shows promise in sub-bandgap sensitization of silicon and other optoelectronic materials, resulting in potential applications ranging from photovoltaics that exceed the Shockley-Queisser limit to infrared imaging. A feasible mechanism for near-infrared-to-visible upconversion is triplet-triplet annihilation (TTA) sensitized by colloidal nanocrystals (NCs). Here, the long lifetime of spin-triplet excitons in the organic materials that undergo TTA makes upconversion possible under incoherent excitation at relatively low photon fluxes. Since this process relies on optically inactive triplet states, semiconductor NCs are utilized as efficient spin mixers, absorbing the incident light and sensitizing the triplet states of the TTA material. The state-of-the-art system uses rubrene with a triplet energy of 1.14 eV as the TTA medium, and thus allows upconversion of light with photon energies above ∼1.1 eV. In this perspective, we review the field of lead sulfide (PbS) NC-sensitized near-infrared-to-visible upconversion, discuss solution-based upconversion, and highlight progress made on solid-state upconversion devices.

Structure and intense UV up-conversion emissions in RE3+-doped sol-gel glass-ceramics containing KYF4 nanocrystals

NASA Astrophysics Data System (ADS)

Yanes, A. C.; Santana-Alonso, A.; Méndez-Ramos, J.; del-Castillo, J.

2013-12-01

Transparent nano-glass-ceramics containing KYF4 nanocrystals were successfully obtained by the sol-gel method, doped with Eu3+ and co-doped with Yb3+ and Tm3+ ions. Precipitation of cubic KYF4 nanocrystals was confirmed by X-ray diffraction and high-resolution transmission electron microscope images. Excitation and emission spectra let us to discern between ions into KYF4 nanocrystals and those remaining in a glassy environment, supplemented with time-resolved photoluminescence decays, that also clearly reveal differences between local environments. Unusual high-energy up-conversion emissions in the UV range were obtained in Yb3+-Tm3+ co-doped samples, and involved mechanisms were discussed. The intensity of these high-energy emissions was analyzed as a function of Yb3+ concentration, heat treatment temperature of precursor sol-gel glasses and pump power, determining the optimum values for potential optical applications as highly efficient UV up-conversion materials in UV solid-state lasers.

The Upconversion Luminescence of Er3+/Yb3+/Nd3+ Triply-Doped β-NaYF4 Nanocrystals under 808-nm Excitation

PubMed Central

Tian, Lijiao; Xu, Zheng; Zhao, Suling; Cui, Yue; Liang, Zhiqin; Zhang, Junjie; Xu, Xurong

2014-01-01

In this paper, Nd3+–Yb3+–Er3+-doped β-NaYF4 nanocrystals with different Nd3+ concentrations are synthesized, and the luminescence properties of the upconversion nanoparticles (UCNPs) have been studied under 808-nm excitation for sensitive biological applications. The upconversion luminescence spectra of NaYF4 nanoparticles with different dopants under 808-nm excitation proves that the Nd3+ ion can absorb the photons effectively, and the Yb3+ ion can play the role of an energy-transfer bridging ion between the Nd3+ ion and Er3+ ion. To investigate the effect of the Nd3+ ion, the decay curves of the 4S3/2 → 4I15/2 transition at 540 nm are measured and analyzed. The NaYF4: 20% Yb3+, 2% Er3+, 0.5% Nd3+ nanocrystals have the highest emission intensity among all samples under 808-nm excitation. The UC (upconversion) mechanism under 808-nm excitation is discussed in terms of the experimental results. PMID:28788246

Plasmon enhanced upconversion luminescence of NaYF4:Yb,Er@SiO2@Ag core-shell nanocomposites for cell imaging

NASA Astrophysics Data System (ADS)

Yuan, Peiyan; Lee, Yih Hong; Gnanasammandhan, Muthu Kumara; Guan, Zhenping; Zhang, Yong; Xu, Qing-Hua

2012-07-01

NaYF4:Yb,Er@SiO2@Ag core-shell nanocomposites were prepared to investigate metal-enhanced upconversion luminescence. Two sizes (15 and 30 nm) of Ag nanoparticles were used. The emission intensity of the upconversion nanocrystals was found to be strongly modulated by the presence of Ag nanoparticles (NPs) on the outer shell layer of the nanocomposites. The extent of modulation depended on the separation distance between Ag NPs and upconversion nanocrystals. The optimum upconversion luminescence enhancement was observed at a separation distance of 10 nm for Ag NPs with two different sizes (15 and 30 nm). A maximum upconversion luminescence enhancement of 14.4-fold was observed when 15 nm Ag nanoparticles were used and 10.8-fold was observed when 30 nm Ag NPs were used. The separation distance dependent emission intensity is ascribed to the competition between energy transfer and enhanced radiative decay rates. The biocompatibility of the nanocomposites was significantly improved by surface modification with DNA. The biological imaging capabilities of these nanocomposites were demonstrated using B16F0 cells.NaYF4:Yb,Er@SiO2@Ag core-shell nanocomposites were prepared to investigate metal-enhanced upconversion luminescence. Two sizes (15 and 30 nm) of Ag nanoparticles were used. The emission intensity of the upconversion nanocrystals was found to be strongly modulated by the presence of Ag nanoparticles (NPs) on the outer shell layer of the nanocomposites. The extent of modulation depended on the separation distance between Ag NPs and upconversion nanocrystals. The optimum upconversion luminescence enhancement was observed at a separation distance of 10 nm for Ag NPs with two different sizes (15 and 30 nm). A maximum upconversion luminescence enhancement of 14.4-fold was observed when 15 nm Ag nanoparticles were used and 10.8-fold was observed when 30 nm Ag NPs were used. The separation distance dependent emission intensity is ascribed to the competition between energy transfer and enhanced radiative decay rates. The biocompatibility of the nanocomposites was significantly improved by surface modification with DNA. The biological imaging capabilities of these nanocomposites were demonstrated using B16F0 cells. Electronic supplementary information (ESI) available: More TEM images, distribution histograms, UV-Vis extinction spectra, and XRD analysis of the core-shell nanocomposites; the emission enhancement mechanisms, bright field images, the effect of DNA modification on the emission; luminescence stability and size changes of the DNA modified nanocomposites in the cell culture. See DOI: 10.1039/c2nr31241g

Plasmon enhanced upconversion luminescence of NaYF4:Yb,Er@SiO2@Ag core-shell nanocomposites for cell imaging.

PubMed

Yuan, Peiyan; Lee, Yih Hong; Gnanasammandhan, Muthu Kumara; Guan, Zhenping; Zhang, Yong; Xu, Qing-Hua

2012-08-21

NaYF(4):Yb,Er@SiO(2)@Ag core-shell nanocomposites were prepared to investigate metal-enhanced upconversion luminescence. Two sizes (15 and 30 nm) of Ag nanoparticles were used. The emission intensity of the upconversion nanocrystals was found to be strongly modulated by the presence of Ag nanoparticles (NPs) on the outer shell layer of the nanocomposites. The extent of modulation depended on the separation distance between Ag NPs and upconversion nanocrystals. The optimum upconversion luminescence enhancement was observed at a separation distance of 10 nm for Ag NPs with two different sizes (15 and 30 nm). A maximum upconversion luminescence enhancement of 14.4-fold was observed when 15 nm Ag nanoparticles were used and 10.8-fold was observed when 30 nm Ag NPs were used. The separation distance dependent emission intensity is ascribed to the competition between energy transfer and enhanced radiative decay rates. The biocompatibility of the nanocomposites was significantly improved by surface modification with DNA. The biological imaging capabilities of these nanocomposites were demonstrated using B16F0 cells.

Highly efficient upconversion luminescence in hexagonal NaYF4:Yb3+, Er3+ nanocrystals synthesized by a novel reverse microemulsion method

NASA Astrophysics Data System (ADS)

Gunaseelan, M.; Yamini, S.; Kumar, G. A.; Senthilselvan, J.

2018-01-01

A new reverse microemulsion system is proposed for the first time to synthesize NaYF4:Yb,Er nanocrystals, which demonstrated high upconversion emission in 550 and 662 nm at 980 nm diode laser excitation. The reverse microemulsion (μEs) system is comprised of CTAB and oleic acid as surfactant and 1-butanol co-surfactant and isooctane oil phase. The surfactant to water ratio is able to tune the microemulsion droplet size from 14 to 220 nm, which eventually controls the crystallinity and particulate morphology of NaYF4:Yb,Er. Also, the microemulsion precursor and calcination temperature plays certain role in transforming the cubic NaYF4:Yb,Er to highly luminescent hexagonal crystal structured upconversion material. Single phase hexagonal NaYF4:YbEr nanorod prepared by water-in-oil reverse microemulsion (μEs) gives intense red upconversion emission. Both nanosphere and nanorod shaped NaYF4:Yb,Er was obtained, but nanorod morphology resulted an enhanced upconversion luminescence. The structural, morphological, thermal and optical luminescence properties of the NaYF4:Yb,Er nanoparticles are discussed in detail by employing powder X-ray diffraction, dynamic light scattering, high resolution electron microscopy, TGA-DTA, UV-DRS, FTIR and photoluminescence spectroscopy. Intense upconversion emission achieved in the microemulsion synthesized NaYF4:Yb3+,Er3+ nanocrystal can make it as useful optical phosphor for solar cell applications.

Hybrid Molecule-Nanocrystal Photon Upconversion Across the Visible and Near-Infrared

DTIC Science & Technology

2015-07-10

applications in solar energy, biological imaging , and data storage. In this Letter, CdSe and PbSe semiconductor nanocrystals are combined with molecular...Goldschmidt, J. C. Absolute Upconversion Quantum Yield of β-NaYF4 Doped with Er3+ and External Quantum Efficiency of Upconverter Solar Cell Devices...C. Peak External Photocurrent Quantum Efficiency Exceeding 100% via MEG in a Quantum Dot Solar Cell . Science 2011, 334, 1530−1533. (37) Choi, J.-H

Multicolor tunability and upconversion enhancement of fluoride nanoparticles by oxygen dopant

NASA Astrophysics Data System (ADS)

Niu, Wenbin; Wu, Suli; Zhang, Shufen; Su, Liap Tat; Tok, Alfred Iing Yoong

2013-08-01

The ability to manipulate the upconversion luminescence of lanthanide-ion doped fluoride upconversion nanoparticles (UCNPs) is particularly important and highly desired due to their wide applications in color displays, multiplexing bioassays and multicolor imaging. Here, we developed a strategy for simultaneously tuning color output and enhancing upconversion emission of Yb/Er doped fluoride UCNPs, based on adjusting the oxygen doping level. The synthesis of multicolored multifunctional NaGdF4:Yb,Er UCNPs was used as the model host system to demonstrate this protocol. Ammonium nitrate (NH4NO3) was used as the oxygen source and added into the reaction system at the beginning stage of nucleation and growth process of fluoride UCNPs, which facilitates the formation of enough oxygen atoms and the diffusion of these into the fluoride host matrix. The results revealed that multicolour output and upconversion enhancement mainly resulted from the variation of phonon energy and crystal field symmetry of the host lattice, respectively. This strategy can be further expanded to other fluoride host matrices. As an example of an application, multicolored UCNPs were used as a color converter in light emitting diodes, which can effectively convert near-infrared light into visible light. It is expected that these multicolored UCNPs will be promising for applications in multiplexing biodetection, bioimaging (optical and magnetic resonance imaging) and other optical technologies, and the present method for the control of O2- doping may also be used in other functional nanomaterials.The ability to manipulate the upconversion luminescence of lanthanide-ion doped fluoride upconversion nanoparticles (UCNPs) is particularly important and highly desired due to their wide applications in color displays, multiplexing bioassays and multicolor imaging. Here, we developed a strategy for simultaneously tuning color output and enhancing upconversion emission of Yb/Er doped fluoride UCNPs, based on adjusting the oxygen doping level. The synthesis of multicolored multifunctional NaGdF4:Yb,Er UCNPs was used as the model host system to demonstrate this protocol. Ammonium nitrate (NH4NO3) was used as the oxygen source and added into the reaction system at the beginning stage of nucleation and growth process of fluoride UCNPs, which facilitates the formation of enough oxygen atoms and the diffusion of these into the fluoride host matrix. The results revealed that multicolour output and upconversion enhancement mainly resulted from the variation of phonon energy and crystal field symmetry of the host lattice, respectively. This strategy can be further expanded to other fluoride host matrices. As an example of an application, multicolored UCNPs were used as a color converter in light emitting diodes, which can effectively convert near-infrared light into visible light. It is expected that these multicolored UCNPs will be promising for applications in multiplexing biodetection, bioimaging (optical and magnetic resonance imaging) and other optical technologies, and the present method for the control of O2- doping may also be used in other functional nanomaterials. Electronic supplementary information (ESI) available: Upconversion spectra of NaYF4:Yb,Er UCNPs prepared with various oxygen sources (trimethylamine N-oxide and ammonium carbonate, Fig. S1) and different addition temperatures of NH4NO3 (Fig. S2), enlarged XRD patterns (Fig. S3), the intensity ratios of green to red emissions of NaGdF4:Yb,Er UCNPs prepared with various amounts of NH4NO3 (Fig. S4), power dependence of upconversion spectra of NaGdF4:Yb,Er UCNPs prepared at 300 °C for 1 h (Fig. S5), upconversion spectra of the product after further reaction between as-prepared NaYF4:Yb,Er and 50 mg of NH4NO3 at 300 °C for 1 h (Fig. S6), XRD patterns of NaYF4:Yb,Er and NaLuF4:Yb,Er UCNPs prepared with various amounts of NH4NO3 (Fig. S7 and S8), the corresponding magnetization curves of NaGdF4:Yb,Er UCNPs (Fig. S9). See DOI: 10.1039/c3nr01612a

Structure and up-conversion luminescence in sol-gel derived Er 3+-Yb 3+ co-doped SiO 2:PbF 2 nano-glass-ceramics

NASA Astrophysics Data System (ADS)

del-Castillo, J.; Yanes, A. C.; Méndez-Ramos, J.; Tikhomirov, V. K.; Rodríguez, V. D.

2009-11-01

Transparent oxyfluoride nano-glass-ceramics 90(SiO 2)10(PbF 2) co-doped with 0.3 Yb 3+ and 0.1 Er 3+ (mol%) have been prepared by thermal treatment of precursor sol-gel glasses. X-ray diffraction and high resolution transmission electron microscopy analysis pointed out a precipitation of cubic β-PbF 2 nanocrystals of certain diameter in nano-glass-ceramics varying from 10 to 20 nm depending on heat treatment conditions. The incorporation of Yb 3+ and Er 3+ dopants in these nanocrystals has been confirmed by signatures of luminescence spectroscopy. Up-conversion luminescence pumped at 980 nm has been detected. Colour tuneability of up-conversion luminescence varying pump power has been analyzed in terms of standard chromaticity diagram. This tuneability opens applications for up-conversion phosphors and three-dimensional optical recording.

Plasmon-enhanced energy transfer for improved upconversion of infrared radiation in doped-lanthanide nanocrystals

NASA Astrophysics Data System (ADS)

Sun, Qi; Mundoor, Haridas; Ribot, Josep; Singh, Vivek; Smalyukh, Ivan; Nagpal, Prashant

2014-03-01

Upconversion of infrared radiation into visible light has been investigated for applications in biological imaging and photovoltaics. However, low conversion efficiency due to small absorption cross-section for infrared light (Yb3+) , and slow rate of energy transfer (to Er3+ states) has prevented application of upconversion photoluminescence (UPL) for diffuse sunlight or imaging tissue samples. Here, we utilize resonant surface plasmon polaritons (SPP) waves to enhance UPL in doped-lanthanide nanocrystals. Our analysis indicates that SPP waves not only enhance the electromagnetic field, and hence weak Purcell effect, but also increases the rate of resonant energy transfer from Yb3+ to Er3+ ions by 6 fold. While we do observe strong metal mediated quenching (14 fold) of green fluorescence on flat metal surfaces, the nanostructured metal is resonant in the infrared, and hence enhances the nanocrystal UPL. This strong columbic effect on energy transfer can have important implications for other fluorescent and excitonic systems too.

CdS/ZnS core-shell nanocrystal photosensitizers for visible to UV upconversion.

PubMed

Gray, Victor; Xia, Pan; Huang, Zhiyuan; Moses, Emily; Fast, Alexander; Fishman, Dmitry A; Vullev, Valentine I; Abrahamsson, Maria; Moth-Poulsen, Kasper; Lee Tang, Ming

2017-08-01

Herein we report the first example of nanocrystal (NC) sensitized triplet-triplet annihilation based photon upconversion from the visible to ultraviolet (vis-to-UV). Many photocatalyzed reactions, such as water splitting, require UV photons in order to function efficiently. Upconversion is one possible means of extending the usable range of photons into the visible. Vis-to-UV upconversion is achieved with CdS/ZnS core-shell NCs as the sensitizer and 2,5-diphenyloxazole (PPO) as annihilator and emitter. The ZnS shell was crucial in order to achieve any appreciable upconversion. From time resolved photoluminescence and transient absorption measurements we conclude that the ZnS shell affects the NC and triplet energy transfer (TET) from NC to PPO in two distinct ways. Upon ZnS growth the surface traps are passivated thus increasing the TET. The shell, however, also acts as a tunneling barrier for TET, reducing the efficiency. This leads to an optimal shell thickness where the upconversion quantum yield ( Φ ' UC ) is maximized. Here the maximum Φ ' UC was determined to be 5.2 ± 0.5% for 4 monolayers of ZnS shell on CdS NCs.

Blue upconversion with excitation into Tm ions at 780 nm in Yb- and Tm-codoped fluoride crystals

NASA Astrophysics Data System (ADS)

Zhang, X. X.; Hong, P.; Bass, M.; Chai, B. H. T.

1995-04-01

Strong blue emissions have been observed in fluoride crystals, such as LiYF4, BaY2F8, and KYF4, codoped with Tm3+ and Yb3+ when excited into the Tm3+ 3F4 state at ~780 nm. Energy transfer from Tm3+ to Yb3+ ions followed by the transfer from Yb3+ to Tm3+ was demonstrated to be responsible for the upconversion process. A pumping scheme is proposed based on this upconversion mechanism for blue-laser applications using these materials.

Formation and transformation of the radiation-induced nearsurface color centers in sodium and lithium fluorides nanocrystals

NASA Astrophysics Data System (ADS)

Novikov, A. N.; Kalinov, V. S.; Radkevich, A. V.; Runets, L. P.; Stupak, A. P.; Voitovich, A. P.

2017-11-01

Near-surface color centers in sodium fluoride nanocrystals have been formed. At pre-irradiation annealing of sodium and lithium fluorides samples at temperatures of 623 K and above, the near-surface color centers in them have not been found after γ-irradiation. Annealing lithium fluoride nanocrystals with the near-surface defects leads to their transformation into bulk ones of the same composition.

Highly intensified upconversion luminescence of Ca(2+) -doped Yb/Er:NaGdF(4) nanocrystals prepared by a solvothermal route.

PubMed

Lei, Lei; Chen, Daqin; Xu, Ju; Zhang, Rui; Wang, Yuansheng

2014-03-01

Upon introducing Ca(2+) dopants into the grain lattices by substituting Gd(3+) ions, irregular Yb/Er:NaGdF4 nanocrystals prepared through a simple solvothermal route convert into highly uniform nanorods. Meanwhile, their upconversion luminescence intensifies by about 200 times, probably due to a modification of the crystal structure of NaGdF4 and an improvement in the crystallinity of the nanophase. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement Photocatalytic Activity of P25 by Modification with a Rare Earth-Free Upconversion Nanocrystal.

PubMed

Yin, Dongguang; Liu, Yumin; Zhao, Feifei; Zhang, Xinyu; Zhang, Tingting; Wu, Chenglong; Chang, Na; Chen, Zhiwen

2018-05-01

It has been reported that coupling TiO2 with rare earth upconversion nanocrystals (UCNCs) is an efficient strategy to significantly improve photocatalytic activity of TiO2. However, the rare earth materials are scarcity and cost, and the synthesis process of UCNCs using the rare earth materials is complicated. In the present study, we have designed a new approach using a rare earth-free upconversion nanocrystal (REF-UCNCs) as upconversion luminescent material to replace the rare earth UCNCs. A novel nanocomposite photocatalyst of REF-UCNCs@P25: Mo/GN was developed for the first time. Based on the designed structure, the REF-UCNCs, Mo-doping, and GN (graphene) have a synergistic effect that can improve catalytic activity of P25 significantly. The results of photocatalytic experiments using RhB as a model pollutant under simulated solar light irradiation show that the photocatalytic efficiency of the as-prepared catalyst is 3-folds higher than that of benchmark substance P25. This work provides a new strategy for efficiently improving catalytic activity of semiconductor photocatalysts by coupling with REF-UCNCs. This approach is facile and low-cost which can be widely applied for modification of semiconductor photocatalysts and facilitates their applications in environmental protection issues using solar light.

Upconversion induced enhancement of dye sensitized solar cells based on core-shell structured β-NaYF4:Er3+, Yb3+@SiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Zhou, Ziyao; Wang, Jiahong; Nan, Fan; Bu, Chenghao; Yu, Zhenhua; Liu, Wei; Guo, Shishang; Hu, Hao; Zhao, Xing-Zhong

2014-01-01

Upconversion materials have been employed as energy relay materials in dye sensitized solar cells (DSCs) to broaden the range of light absorption. However, the origin of the enhancements can be induced by both upconversion and size-dependent light scattering effects. To clarify the role of the upconversion material in the photoelectrode of DSCs, an upconversion induced device was realized here, which has the size-dependent light scattering effect eliminated via the application of NaYF4:Er3+, Yb3+@SiO2 upconversion nanoparticles (β-NYEY@SiO2 UCNPs). An enhancement of 6% in efficiency was observed for the device. This demonstration provided an insight into the possible further employment of upconversion in DSCs.Upconversion materials have been employed as energy relay materials in dye sensitized solar cells (DSCs) to broaden the range of light absorption. However, the origin of the enhancements can be induced by both upconversion and size-dependent light scattering effects. To clarify the role of the upconversion material in the photoelectrode of DSCs, an upconversion induced device was realized here, which has the size-dependent light scattering effect eliminated via the application of NaYF4:Er3+, Yb3+@SiO2 upconversion nanoparticles (β-NYEY@SiO2 UCNPs). An enhancement of 6% in efficiency was observed for the device. This demonstration provided an insight into the possible further employment of upconversion in DSCs. Electronic supplementary information (ESI) available: Details of preparations and characterizations; the TEM images, EDX measurements, XRD measurements and upconversion emission spectrum of bared β-NYEY nanocrystals; SEM and AFM images of the photoelectrode with different concentrations of β-NYEY nanocrystals; J-V characteristics, EIS measurements and fitted EIS parameters of the DSCs based on five different photoelectrodes. See DOI: 10.1039/c3nr04315k

Highly efficient up-conversion and bright white light in RE co-doped KYF4 nanocrystals in sol-gel silica matrix

NASA Astrophysics Data System (ADS)

Méndez-Ramos, J.; Yanes, A. C.; Santana-Alonso, A.; del-Castillo, J.

2013-01-01

Transparent nano-glass-ceramics comprising Yb3+, Er3+ and Tm3+ co-doped KYF4 nanocrystals have been developed from sol-gel method. A structural analysis by means of X-ray diffraction confirmed the precipitation of cubic KYF4 nanocrystals into a silica matrix. Visible luminescence has been analyzed as function of treatment temperature of precursor sol-gel glasses. Highly efficient up-conversion emissions have been obtained under 980 nm excitation and studied by varying the doping level, processing temperature and pump power. Color tuneability has been quantified in terms of CIE diagram and in particular, a white-balanced overall emission has been achieved for a certain doping level and thermal treatment.

Effect of various surfactants on changes in the emission color chromaticity in upconversion YVO4: Yb3+, Er3+ nanoparticles

NASA Astrophysics Data System (ADS)

Woźny, Przemysław; Szczeszak, Agata; Lis, Stefan

2018-02-01

YVO4: Yb3+,Er3+ upconverting nanocrystals were synthesized via a hydrothermal method using different compounds as surfactants. Structure and morphology of the nanocrystals were investigated by X-ray diffraction and transmission electron microscopy. Tetragonal crystal structure of the nanocrystals appeared irrespective of the type of surfactant used. The average crystallite size was estimated by TEM images. The obtained products were composed of small nanoparticles, in the size range of 10-60 nm, depending on the surfactant used. The morphology of the nanoparticles was also regulated by the type of surfactant. Spectroscopic analysis of the materials obtained was carried out by measuring the emission and excitation spectra and the intensity of luminescence as a function of laser energy and luminescence decays. The nanocrystals prepared exhibited a green upconversion emission attributed to the 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 transitions of Er3+, under NIR (985 nm) pulse laser irradiation, and their emission lifetimes were in the range 3.84-4.90 μs. On the basis of the spectroscopic investigation, the upconversion mechanism was proposed and chromaticity coordinates were calculated. Surfactants were found to influence on chromaticity of luminescence.

Enhancing multiphoton upconversion through energy clustering at sublattice level

NASA Astrophysics Data System (ADS)

Wang, Juan; Deng, Renren; MacDonald, Mark A.; Chen, Bolei; Yuan, Jikang; Wang, Feng; Chi, Dongzhi; Andy Hor, Tzi Sum; Zhang, Peng; Liu, Guokui; Han, Yu; Liu, Xiaogang

2014-02-01

The applications of lanthanide-doped upconversionnanocrystals in biological imaging, photonics, photovoltaics and therapeutics have fuelled a growing demand for rational control over the emission profiles of the nanocrystals. A common strategy for tuning upconversion luminescence is to control the doping concentration of lanthanide ions. However, the phenomenon of concentration quenching of the excited state at high doping levels poses a significant constraint. Thus, the lanthanide ions have to be stringently kept at relatively low concentrations to minimize luminescence quenching. Here we describe a new class of upconversion nanocrystals adopting an orthorhombic crystallographic structure in which the lanthanide ions are distributed in arrays of tetrad clusters. Importantly, this unique arrangement enables the preservation of excitation energy within the sublattice domain and effectively minimizes the migration of excitation energy to defects, even in stoichiometric compounds with a high Yb3+ content (calculated as 98 mol%). This allows us to generate an unusual four-photon-promoted violet upconversion emission from Er3+ with an intensity that is more than eight times higher than previously reported. Our results highlight that the approach to enhancing upconversion through energy clustering at the sublattice level may provide new opportunities for light-triggered biological reactions and photodynamic therapy.

NaGd(MoO4)2 nanocrystals with diverse morphologies: controlled synthesis, growth mechanism, photoluminescence and thermometric properties.

PubMed

Li, Anming; Xu, Dekang; Lin, Hao; Yang, Shenghong; Shao, Yuanzhi; Zhang, Yueli

2016-08-10

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly, and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu(3+) nanocrystals, and upconversion photoluminescence properties of NaGd(MoO4)2: Yb(3+)/Er(3+) and Yb(3+)/Tm(3+) nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift, and the luminescence intensities and lifetimes of Eu(3+) are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb(3+)/Er(3+), Yb(3+)/Tm(3+) nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb(3+)/Er(3+) nanoplates are investigated, and the maximum sensitivity is determined to be 0.01333 K(-1) at 285 K.

NaGd(MoO4)2 nanocrystals with diverse morphologies: controlled synthesis, growth mechanism, photoluminescence and thermometric properties

PubMed Central

Li, Anming; Xu, Dekang; Lin, Hao; Yang, Shenghong; Shao, Yuanzhi; Zhang, Yueli

2016-01-01

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly, and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu3+ nanocrystals, and upconversion photoluminescence properties of NaGd(MoO4)2: Yb3+/Er3+ and Yb3+/Tm3+ nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift, and the luminescence intensities and lifetimes of Eu3+ are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb3+/Er3+, Yb3+/Tm3+ nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb3+/Er3+ nanoplates are investigated, and the maximum sensitivity is determined to be 0.01333 K−1 at 285 K. PMID:27506629

Down- and up-conversion emissions in Er-doped transparent fluorotellurite glass-ceramics

NASA Astrophysics Data System (ADS)

Miguel, A.; Morea, R.; Gonzalo, J.; Fernandez, J.; Balda, R.

2015-03-01

In this work, we report the near infrared and upconversion emissions of Er3+-doped transparent fluorotellurite glassceramics obtained by heat treatment of the precursor Er-doped TeO2-ZnO-ZnF2 glass. Structural analysis shows that ErF3 nanocrystals nucleated in the glass-ceramic sample are homogeneously distributed in the glass matrix with a typical size of 45±10 nm. The comparison of the fluorescence properties of Er3+-doped precursor glass and glass-ceramic confirms the successful incorporation of the rare-earth into the nanocrystals. An enhancement of the red upconversion emission due to 4F9/2→4I15/2 transition together with weak emission bands due to transitions from 2H9/2, 4F3/2,5/2, and 4F7/2 levels to the ground state are observed under excitation at 801 nm in the glass-ceramic sample. The temporal evolution of the red emission together with the excitation upconversion spectrum suggest that energy transfer processes are responsible for the enhancement of the red emission.

Luminescence of Er 3+-doped nanostructured SiO 2-LaF 3 glass-ceramics prepared by the sol-gel method

NASA Astrophysics Data System (ADS)

Rodríguez, V. D.; Del Castillo, J.; Yanes, A. C.; Méndez-Ramos, J.; Torres, M.; Peraza, J.

2007-07-01

Transparent glass ceramics with composition of 95SiO2-5LaF3 doped with 0.1 mol% of Er3+ were synthesized by thermal treatment of precursor sol-gel glasses. Segregated LaF3 nanocrystals in the glass were confirmed from a structural analysis performed by X-ray diffraction. Blue, green and red efficient up-conversion emissions were observed under 980 nm excitation at room temperature. Under this excitation near infrared down-conversion at 1.55 μm is also observed. These results could be attributed to the precipitation of LaF3 nanocrystals and the incorporation of most Er3+ ions in these nanocrystals. The mechanisms involved in the up-conversion emissions could be ascribed to two and three photon processes.

Intense blue up-conversion luminescence in Tm 3+/Yb 3+ codoped oxyfluoride glass-ceramics containing β-PbF 2 nanocrystals

NASA Astrophysics Data System (ADS)

Zhang, Junjie; Duan, Zhongchao; He, Dongbing; Dai, Shixun; Zhang, Liyan; Hu, Lili

2005-12-01

Up-conversion luminescence properties of a Tm 3+/Yb 3+ codoped oxyfluoride glass-ceramics under 980 nm excitation are investigated. Intense blue emission centered at 476 nm, corresponding to 1G 4 → 3H 6 transitions of Tm 3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF 3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense Tm 3+ up-conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated.

Intense blue up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics containing beta-PbF2 nanocrystals.

PubMed

Zhang, Junjie; Duan, Zhongchao; He, Dongbing; Dai, Shixun; Zhang, Liyan; Hu, Lili

2005-12-01

Up-conversion luminescence properties of a Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation are investigated. Intense blue emission centered at 476 nm, corresponding to 1G4-->3H6 transitions of Tm3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated.

The aggregation and characteristics of radiation-induced defects in lithium fluoride nanocrystals

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Korzhik, M. V.; Martynovich, E. F.; Runets, L. P.; Stupak, A. P.

2013-02-01

It has been established that diffusion activation energies for anion vacancies and centres ? in lithium fluoride nanocrystals are higher than those in bulk crystals. In nanocrystals, ? centres migrating in the range of the temperature close to room temperature is not observed and these centres remain stable. The ratio of centres ? and F 2 concentrations in nanocrystals is higher than in bulk crystals. A new type of colour centres, which is absent in bulk crystals, is discovered in nanocrystals.

Characterization and cysteine sensing performance of nanocomposites based on up-conversion excitation host and rhodamine-derived probes

NASA Astrophysics Data System (ADS)

Yuqing, Zhao; Yi, Xing; Lihua, Li; Juanjuan, Ma

2018-02-01

Optical sensing for cysteine (Cys) recognition is an interesting topic due to Cys biological participation. In this paper, two rhodamine-based chemosensors were designed for Cys optical sensing. For chemosensor photostability improvement, up-conversion nanocrystals were synthesized and used as excitation host. These nanocrystals were modified with a phase transfer reagent α-cyclodextrin (α-CD) to improve their compatibility with chemosensors. An efficient energy transfer from these nanocrystals to chemosensors under 980 nm radiation was observed and confirmed by spectral match analysis, energy transfer radius calculation and emission decay lifetime comparison. A direct bonding mechanism between Cys and chemosensors with bonding stoichiometry of 1:1 was established by Job's plot experiment. Given the presence of Cys, chemosensor emission was increased, showing emission turn on effect. These two chemosensors showed good selectivity, improved photostability and linear sensing response towards Cys.

Laser refrigeration of hydrothermal nanocrystals in physiological media.

PubMed

Roder, Paden B; Smith, Bennett E; Zhou, Xuezhe; Crane, Matthew J; Pauzauskie, Peter J

2015-12-08

Coherent laser radiation has enabled many scientific and technological breakthroughs including Bose-Einstein condensates, ultrafast spectroscopy, superresolution optical microscopy, photothermal therapy, and long-distance telecommunications. However, it has remained a challenge to refrigerate liquid media (including physiological buffers) during laser illumination due to significant background solvent absorption and the rapid (∼ ps) nonradiative vibrational relaxation of molecular electronic excited states. Here we demonstrate that single-beam laser trapping can be used to induce and quantify the local refrigeration of physiological media by >10 °C following the emission of photoluminescence from upconverting yttrium lithium fluoride (YLF) nanocrystals. A simple, low-cost hydrothermal approach is used to synthesize polycrystalline particles with sizes ranging from <200 nm to >1 μm. A tunable, near-infrared continuous-wave laser is used to optically trap individual YLF crystals with an irradiance on the order of 1 MW/cm(2). Heat is transported out of the crystal lattice (across the solid-liquid interface) by anti-Stokes (blue-shifted) photons following upconversion of Yb(3+) electronic excited states mediated by the absorption of optical phonons. Temperatures are quantified through analysis of the cold Brownian dynamics of individual nanocrystals in an inhomogeneous temperature field via forward light scattering in the back focal plane. The cold Brownian motion (CBM) analysis of individual YLF crystals indicates local cooling by >21 °C below ambient conditions in D2O, suggesting a range of potential future applications including single-molecule biophysics and integrated photonic, electronic, and microfluidic devices.

Laser refrigeration of hydrothermal nanocrystals in physiological media

PubMed Central

Roder, Paden B.; Smith, Bennett E.; Zhou, Xuezhe; Crane, Matthew J.; Pauzauskie, Peter J.

2015-01-01

Coherent laser radiation has enabled many scientific and technological breakthroughs including Bose–Einstein condensates, ultrafast spectroscopy, superresolution optical microscopy, photothermal therapy, and long-distance telecommunications. However, it has remained a challenge to refrigerate liquid media (including physiological buffers) during laser illumination due to significant background solvent absorption and the rapid (∼ps) nonradiative vibrational relaxation of molecular electronic excited states. Here we demonstrate that single-beam laser trapping can be used to induce and quantify the local refrigeration of physiological media by >10 °C following the emission of photoluminescence from upconverting yttrium lithium fluoride (YLF) nanocrystals. A simple, low-cost hydrothermal approach is used to synthesize polycrystalline particles with sizes ranging from <200 nm to >1 μm. A tunable, near-infrared continuous-wave laser is used to optically trap individual YLF crystals with an irradiance on the order of 1 MW/cm2. Heat is transported out of the crystal lattice (across the solid–liquid interface) by anti-Stokes (blue-shifted) photons following upconversion of Yb3+ electronic excited states mediated by the absorption of optical phonons. Temperatures are quantified through analysis of the cold Brownian dynamics of individual nanocrystals in an inhomogeneous temperature field via forward light scattering in the back focal plane. The cold Brownian motion (CBM) analysis of individual YLF crystals indicates local cooling by >21 °C below ambient conditions in D2O, suggesting a range of potential future applications including single-molecule biophysics and integrated photonic, electronic, and microfluidic devices. PMID:26589813

Highly efficient green up-conversion luminescence of Nd3+-Yb3+-Ho3+ codoped fluorite-type nanocrystals in transparent glass ceramics

NASA Astrophysics Data System (ADS)

Qiu, Jianbei; Kawamoto, Yoji; Zhang, Junjie

2002-11-01

Oxyfluoride glasses were developed with composition 30SiO2[middle dot]15AlO1.5[middle dot]28PbF2[middle dot]22CdF2[middle dot](4.8-x)GdF3[middle dot]0.1NdF3[middle dot]0.1HoF3[middle dot]xYbF3 (x=0, 0.1, 0.2, 0.5, 1, 2, 3, 4, and 4.8) in mole percent. Powder x-ray diffraction analysis revealed that the heat treatments of the oxyfluoride glasses at 450 degC for 0.5 h cause the precipitation of Nd3+-Yb3+-Ho3+ codoped fluorite-type nanocrystals of about 16.3 nm in diameter in the glass matrix. These transparent glass ceramics exhibited very strong green up-conversion luminescence due to the Ho3+: (5F4, 5S2)[right arrow]5I8 transition under 800 nm excitation. The intensity of the green up-conversion luminescence in a 1 mol % YbF3-containing glass ceramic was found to be about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho3+ up-conversion luminescence in the oxyfluoride glass ceramics is discussed. An up-conversion mechanism is also proposed.

``Smart'' theranostic lanthanide nanoprobes with simultaneous up-conversion fluorescence and tunable T1-T2 magnetic resonance imaging contrast and near-infrared activated photodynamic therapy

NASA Astrophysics Data System (ADS)

Zhang, Yan; Das, Gautom Kumar; Vijayaragavan, Vimalan; Xu, Qing Chi; Padmanabhan, Parasuraman; Bhakoo, Kishore K.; Tamil Selvan, Subramanian; Tan, Timothy Thatt Yang

2014-10-01

The current work reports a type of ``smart'' lanthanide-based theranostic nanoprobe, NaDyF4:Yb3+/NaGdF4:Yb3+,Er3+, which is able to circumvent the up-converting poisoning effect of Dy3+ ions to give efficient near infrared (980 nm) triggered up-conversion fluorescence, and offers not only excellent dark T2-weighted MR contrast but also tunable bright and T1-weighted MR contrast properties. Due to the efficient up-converted energy transfer from the nanocrystals to chlorin e6 (Ce6) photosensitizers loaded onto the nanocrystals, cytotoxic singlet oxygen was generated and photodynamic therapy was demonstrated. Therefore, the current multifunctional nanocrystals could be potentially useful in various image-guided diagnoses where bright or dark MRI contrast could be selectively tuned to optimize image quality, but also as an efficient and more penetrative near-infrared activated photodynamic therapy agent.The current work reports a type of ``smart'' lanthanide-based theranostic nanoprobe, NaDyF4:Yb3+/NaGdF4:Yb3+,Er3+, which is able to circumvent the up-converting poisoning effect of Dy3+ ions to give efficient near infrared (980 nm) triggered up-conversion fluorescence, and offers not only excellent dark T2-weighted MR contrast but also tunable bright and T1-weighted MR contrast properties. Due to the efficient up-converted energy transfer from the nanocrystals to chlorin e6 (Ce6) photosensitizers loaded onto the nanocrystals, cytotoxic singlet oxygen was generated and photodynamic therapy was demonstrated. Therefore, the current multifunctional nanocrystals could be potentially useful in various image-guided diagnoses where bright or dark MRI contrast could be selectively tuned to optimize image quality, but also as an efficient and more penetrative near-infrared activated photodynamic therapy agent. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01717j

[A study on the concentration quenching of Tm3+ upconversion luminescence].

PubMed

Chen, B; Wang, H; Huang, S

2001-06-01

In this work, we have a designation and preparation of MFT glasses for upconversion, the glasses consisted of TeO2 and fluoride: PbF2, AlF3, BaF2, NaF and the impurity Tm2O3. In this glass system the oxide improve forming ability, the fluorides improve the microscopic environment around RE ions in glasses. In this glass host the content of Tm2O3 achieves to 4% mol and crystallization no occurred. A detail study on the concentration quenching of upconversion luminescence for 1G4-->3H6 and 1D2-->3H4 transitions was completed. The experimental results directed that the quenching concentration was 0.6 mol.% and higher 3 times than in other glasses materials. The cross relaxation and mechanism of concentration quenching were discussed.

"Smart" theranostic lanthanide nanoprobes with simultaneous up-conversion fluorescence and tunable T1-T2 magnetic resonance imaging contrast and near-infrared activated photodynamic therapy.

PubMed

Zhang, Yan; Das, Gautom Kumar; Vijayaragavan, Vimalan; Xu, Qing Chi; Padmanabhan, Parasuraman; Bhakoo, Kishore K; Selvan, Subramanian Tamil; Tan, Timothy Thatt Yang

2014-11-07

The current work reports a type of "smart" lanthanide-based theranostic nanoprobe, NaDyF4:Yb(3+)/NaGdF4:Yb(3+),Er(3+), which is able to circumvent the up-converting poisoning effect of Dy(3+) ions to give efficient near infrared (980 nm) triggered up-conversion fluorescence, and offers not only excellent dark T2-weighted MR contrast but also tunable bright and T1-weighted MR contrast properties. Due to the efficient up-converted energy transfer from the nanocrystals to chlorin e6 (Ce6) photosensitizers loaded onto the nanocrystals, cytotoxic singlet oxygen was generated and photodynamic therapy was demonstrated. Therefore, the current multifunctional nanocrystals could be potentially useful in various image-guided diagnoses where bright or dark MRI contrast could be selectively tuned to optimize image quality, but also as an efficient and more penetrative near-infrared activated photodynamic therapy agent.

An Anion-Induced Hydrothermal Oriented-Explosive Strategy for the Synthesis of Porous Upconversion Nanocrystals

PubMed Central

Qiu, Peiyu; Sun, Rongjin; Gao, Guo; Zhang, Chunlei; Chen, Bin; Yan, Naishun; Yin, Ting; Liu, Yanlei; Zhang, Jingjing; Yang, Yao; Cui, Daxiang

2015-01-01

Rare-earth (RE)-doped upconversion nanocrystals (UCNCs) are deemed as the promising candidates of luminescent nanoprobe for biological imaging and labeling. A number of methods have been used for the fabrication of UCNCs, but their assembly into porous architectures with desired size, shape and crystallographic phase remains a long-term challenging task. Here we report a facile, anion-induced hydrothermal oriented-explosive method to simultaneously control size, shape and phase of porous UCNCs. Our results confirmed the anion-induced hydrothermal oriented-explosion porous structure, size and phase transition for the cubic/hexagonal phase of NaLuF4 and NaGdF4 nanocrystals with various sizes and shapes. This general method is very important not only for successfully preparing lanthanide doped porous UCNCs, but also for clarifying the formation process of porous UCNCs in the hydrothermal system. The synthesized UCNCs were used for in vitro and in vivo CT imaging, and could be acted as the potential CT contrast agents. PMID:25767613

Nd3+/Yb3+ cascade-sensitized single-band red upconversion emission in active-core/active-shell nanocrystals.

PubMed

Ding, M Y; Hou, J J; Yuan, Y J; Bai, W F; Lu, C H; Xi, J H; Ji, Z G; Chen, D Q

2018-08-24

Lanthanide-doped upconversion nanomaterials (UCNMs) have promoted extensive interest for its biological research and biomedical applications, benefiting from low autofluorescence background, deep light penetration depth, and minimal photo-damage to biological tissues. However, owing to the 980 nm laser-induced overheating issue and the attenuation effect associated with conventional multi-peak emissions, the usage of UCNMs as fluorescent bioprobes is still limited. To address these issues, an effective strategy has been proposed to tune both the excitation and emission peaks of UCNMs into the first biological window (650 ∼ 900 nm), where the light absorption by water and hemoglobin in biological tissues is minimal. Based on the Nd 3+ /Yb 3+ cascade-sensitized upconversion process and efficient exchange-energy transfer between Mn 2+ and Er 3+ in conjunction with the active-core@active-shell nanostructured design, we have developed a new class of upconversion nanoparticles (UCNPs) that exhibit strong single-band red emission upon excitation of an 808 nm near-infrared laser. Hopefully, the well-designed KMnF 3 :Yb/Er/Nd@ KMnF 3 :Yb/Nd core-shell nanocrystals will be considered a promising alternative to conventionally used UCNPs for biolabeling applications without the concern of the overheating issue and the attenuation constraints.

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications.

PubMed

Ai, Xiangzhao; Lyu, Linna; Mu, Jing; Hu, Ming; Wang, Zhimin; Xing, Bengang

2017-11-10

Lanthanide-doped upconversion nanocrystals (UCNs) have attracted much attention in recent years based on their promising and controllable optical properties, which allow for the absorption of near-infrared (NIR) light and can subsequently convert it into multiplexed emissions that span over a broad range of regions from the UV to the visible to the NIR. This article presents detailed experimental procedures for high-temperature co-precipitation synthesis of core-shell UCNs that incorporate different lanthanide ions into nanocrystals for efficiently converting deep-tissue penetrable NIR excitation (808 nm) into a strong blue emission at 480 nm. By controlling the surface modification with biocompatible polymer (polyacrylic acid, PAA), the as-prepared UCNs acquires great solubility in buffer solutions. The hydrophilic nanocrystals are further functionalized with specific ligands (dibenzyl cyclooctyne, DBCO) for localization on the cell membrane. Upon NIR light (808 nm) irradiation, the upconverted blue emission can effectively activate the light-gated channel protein on the cell membrane and specifically regulate the cation (e.g., Ca 2+ ) influx in the cytoplasm. This protocol provides a feasible methodology for the synthesis of core-shell lanthanide-doped UCNs and subsequent biocompatible surface modification for further cellular applications.

Nanocrystals feel the heat

NASA Astrophysics Data System (ADS)

Liang, Liangliang; Liu, Xiaogang

2018-03-01

Phosphors often suffer luminescence quenching at elevated temperatures. Now, thermal quenching can be combated with surface phonon-assisted energy transfer, enabling the luminescence of ultrasmall upconversion nanophosphors to be dramatically enhanced.

A broadening temperature sensitivity range with a core-shell YbEr@YbNd double ratiometric optical nanothermometer

NASA Astrophysics Data System (ADS)

Marciniak, L.; Prorok, K.; Francés-Soriano, L.; Pérez-Prieto, J.; Bednarkiewicz, A.

2016-02-01

The chemical architecture of lanthanide doped core-shell up-converting nanoparticles can be engineered to purposely design the properties of luminescent nanomaterials, which are typically inaccessible to their homogeneous counterparts. Such an approach allowed to shift the up-conversion excitation wavelength from ~980 to the more relevant ~808 nm or enable Tb or Eu up-conversion emission, which was previously impossible to obtain or inefficient. Here, we address the issue of limited temperature sensitivity range of optical lanthanide based nano-thermometers. By covering Yb-Er co-doped core nanoparticles with the Yb-Nd co-doped shell, we have intentionally combined temperature dependent Er up-conversion together with temperature dependent Nd --> Yb energy transfer, and thus have expanded the temperature response range ΔT of a single nanoparticle based optical nano-thermometer under single ~808 nm wavelength photo-excitation from around ΔT = 150 K to over ΔT = 300 K (150-450 K). Such engineered nanocrystals are suitable for remote optical temperature measurements in technology and biotechnology at the sub-micron scale.The chemical architecture of lanthanide doped core-shell up-converting nanoparticles can be engineered to purposely design the properties of luminescent nanomaterials, which are typically inaccessible to their homogeneous counterparts. Such an approach allowed to shift the up-conversion excitation wavelength from ~980 to the more relevant ~808 nm or enable Tb or Eu up-conversion emission, which was previously impossible to obtain or inefficient. Here, we address the issue of limited temperature sensitivity range of optical lanthanide based nano-thermometers. By covering Yb-Er co-doped core nanoparticles with the Yb-Nd co-doped shell, we have intentionally combined temperature dependent Er up-conversion together with temperature dependent Nd --> Yb energy transfer, and thus have expanded the temperature response range ΔT of a single nanoparticle based optical nano-thermometer under single ~808 nm wavelength photo-excitation from around ΔT = 150 K to over ΔT = 300 K (150-450 K). Such engineered nanocrystals are suitable for remote optical temperature measurements in technology and biotechnology at the sub-micron scale. Electronic supplementary information (ESI) available: Characterization, structural and morphological characterization of nanocrystals, the measurement setup. See DOI: 10.1039/c5nr08223d

Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

NASA Astrophysics Data System (ADS)

Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

2016-10-01

Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

All-inorganic colloidal upconversion quantum dots (Conference Presentation)

NASA Astrophysics Data System (ADS)

Oron, Dan; Teitelboim, Ayelet

2017-02-01

Upconversion (UC) is a nonlinear process in which two, or more, long wavelength photons are converted to a shorter wavelength photon. This process is based on sequential absorption of two or more photons, involving metastable, long lived intermediate energy states, thus is not restricted to ultrashort pulsed excitation. Hence, requirements for UC processes are long lived excited states, a ladder like arrangement of energy levels and a mechanism inhibiting cooling of the hot charge carrier. UC holds great promise for bioimaging, enabling to perform multiphoton imaging in scattering specimen at very low powers. Rare-earth-doped nanocrystals, the most commonly used ones for UC, typically require a minimal particle diameter of several tens of nanometers and have a limited action spectrum. Here, we present a novel luminescence upconversion nano-system based on colloidal semiconductor double quantum dots, consisting of a NIR-absorbing component and a visible emitting component separated by a tunneling barrier in a spherical onion-like geometry. These dual near-infrared and visible core/shell/shell PbSe/CdSe/CdS nanocrystals are shown to efficiently upconvert a broad range of NIR wavelengths up to 1.2 microns to visible emission at room temperature, covering a spectral range where there are practically no alternative upconversion systems. The particle diameter is less than ten nanometers, and the synthesis enables versatility and tunability of both the visible emission color and the NIR absorption edge. The physical mechanism for upconversion in this type of structures, as well as potential advances and extensions on this system will be discussed.

White light upconversion emission in Yb3+/ Er3+/ Tm3+ codoped oxy-fluoride lithium tungsten tellurite glass ceramics

NASA Astrophysics Data System (ADS)

Ansari, Ghizal F.; Mahajan, S. K.

2012-02-01

The bright white upconversion emission ( tri-colour UC) is generated in Er/Tm/Yb tri -doped oxy-fluoride lithium tungsten tellurite (TWLOF)glass ceramics containing crystalline phase LiYbF4 under the excitation of 980nm laser diode. The most appropriate combination of rare-earth ions (2mol% YbF3 1mol% ErF3 and 1mol%TmF3 )of glass ceramic sample has been determined to tune the primary colour (RGB and generate white light emission. By varying the pump power, intense and weak blue (487nm, 437nm), green (525nm and 545nm) and red (662nm) emission are simultaneously observed at room temperature. The dependence of upconversion emission intensity suggest that a theephoton process is responsible for the blue emission of Tm3+ ions and red emission due to both Tm3+ and Er3+ ions , while green emission originated from two photon processes in Er3+ ions. Also tri colour upconvesion and energy transfer in this glass ceramics sample were studied under 808nm laser diode excitation. The Upconversion mechanisms and Tm3+ ions plays role of both emitter and activator (transfer energy to Er) were discussed.

Instantaneous ballistic velocity of suspended Brownian nanocrystals measured by upconversion nanothermometry

NASA Astrophysics Data System (ADS)

Brites, Carlos D. S.; Xie, Xiaoji; Debasu, Mengistie L.; Qin, Xian; Chen, Runfeng; Huang, Wei; Rocha, João; Liu, Xiaogang; Carlos, Luís D.

2016-10-01

Brownian motion is one of the most fascinating phenomena in nature. Its conceptual implications have a profound impact in almost every field of science and even economics, from dissipative processes in thermodynamic systems, gene therapy in biomedical research, artificial motors and galaxy formation to the behaviour of stock prices. However, despite extensive experimental investigations, the basic microscopic knowledge of prototypical systems such as colloidal particles in a fluid is still far from being complete. This is particularly the case for the measurement of the particles' instantaneous velocities, elusive due to the rapid random movements on extremely short timescales. Here, we report the measurement of the instantaneous ballistic velocity of Brownian nanocrystals suspended in both aqueous and organic solvents. To achieve this, we develop a technique based on upconversion nanothermometry. We find that the population of excited electronic states in NaYF4:Yb/Er nanocrystals at thermal equilibrium can be used for temperature mapping of the nanofluid with great thermal sensitivity (1.15% K-1 at 296 K) and a high spatial resolution (<1 μm). A distinct correlation between the heat flux in the nanofluid and the temporal evolution of Er3+ emission allows us to measure the instantaneous velocity of nanocrystals with different sizes and shapes.

Rare Earth Ion-Doped Upconversion Nanocrystals: Synthesis and Surface Modification

PubMed Central

Chang, Hongjin; Xie, Juan; Zhao, Baozhou; Liu, Botong; Xu, Shuilin; Ren, Na; Xie, Xiaoji; Huang, Ling; Huang, Wei

2014-01-01

The unique luminescent properties exhibited by rare earth ion-doped upconversion nanocrystals (UCNPs), such as long lifetime, narrow emission line, high color purity, and high resistance to photobleaching, have made them widely used in many areas, including but not limited to high-resolution displays, new-generation information technology, optical communication, bioimaging, and therapy. However, the inherent upconversion luminescent properties of UCNPs are influenced by various parameters, including the size, shape, crystal structure, and chemical composition of the UCNPs, and even the chosen synthesis process and the surfactant molecules used. This review will provide a complete summary on the synthesis methods and the surface modification strategies of UCNPs reported so far. Firstly, we summarize the synthesis methodologies developed in the past decades, such as thermal decomposition, thermal coprecipitation, hydro/solvothermal, sol-gel, combustion, and microwave synthesis. In the second part, five main streams of surface modification strategies for converting hydrophobic UCNPs into hydrophilic ones are elaborated. Finally, we consider the likely directions of the future development and challenges of the synthesis and surface modification, such as the large-scale production and actual applications, stability, and so on, of the UCNPs. PMID:28346995

Broadband dye-sensitized upconverting nanocrystals enabled near-infrared planar perovskite solar cells

NASA Astrophysics Data System (ADS)

Lai, Xuesen; Li, Xitao; Lv, Xinding; Zheng, Yan-Zhen; Meng, Fanli; Tao, Xia

2017-12-01

Extending the spectral absorption of perovskite solar cells (PSCs) from visible into near-infrared (NIR) range is a promising strategy to minimize non-absorption loss of solar photons and enhance the cell photovoltaic performance. Herein, we report on for the first time a viable strategy of incorporating IR806 dye-sensitized upconversion nanocrystals (IR806-UCNCs) into planar PSC for broadband upconversion of NIR light (800-1000 nm) into perovskite absorber-responsive visible emissions. A smart trick is firstly adopted to prepare hydrophilic IR806-UCNCs via a NOBF4 assisted two-step ligand-exchange that allows incorporating with perovskite precursor for in-situ growth of upconverting planar perovskite film. Unlike typically reported upconverting nanoparticles with narrow NIR absorption, the as-prepared IR806-UCNCs are able to harvest NIR light broadly and then transfer the captured energy to the UCNCs for an efficient visible upconversion. The IR806-UCNCs-incorporated cell exhibits a power conversion efficiency of 17.49%, corresponding to 29% increment from that of the pristine cell (13.52%). This strategy provides a feasible way to enable the most efficient harvesting of NIR sunlight for solar cells and other optoelectric devices.

Tuning the morphology, luminescence and magnetic properties of hexagonal-phase NaGdF4: Yb, Er nanocrystals via altering the addition sequence of the precursors

NASA Astrophysics Data System (ADS)

Zhao, Shuwen; Xia, Donglin; Zhao, Ruimin; Zhu, Hao; Zhu, Yiru; Xiong, Yuda; Wang, Youfa

2017-01-01

Hexagonal-phase NaGdF4: Yb, Er upconversion nanocrystals (UCNCs) with tunable morphology and properties were successfully prepared via a thermal decomposition method. The influences of the adding sequence of the precursors on the morphology, chemical composition, luminescence and magnetic properties were investigated by transmission electron microscopy (TEM), inductively coupled plasma-atomic emission spectrometry (ICP-AES), upconversion (UC) spectroscopy, and a vibrating sample magnetometer (VSM). It was found that the resulting nanocrystals, with different sizes ranging from 24 to 224 nm, are in the shape of spheres, hexagonal plates and flakes; moreover, the composition percentage of Yb3+-Er3+ and Gd3+ ions was found to vary in a regular pattern with the adding sequence. Furthermore, the intensity ratios of emission colors (f g/r, f g/p), and the magnetic mass susceptibility of hexagonal-phase NaGdF4: Yb, Er nanocrystals change along with the composition of the nanocrystals. A positive correlation between the susceptibility and f g/r of NaGdF4: Yb, Er was proposed. The decomposition processes of the precursors were investigated by a thermogravimetric (TG) analyzer. The result indicated that the decomposition of the resolved lanthanide trifluoroacetate is greatly different from lanthanide trifluoroacetate powder. It is of tremendous help to recognize the decomposition process of the precursors and to understand the related reaction mechanism.

Ligand Enhanced Upconversion of Near-Infrared Photons with Nanocrystal Light Absorbers

DTIC Science & Technology

2016-03-04

www.rsc.org/chemicalscience This journal is © The Royal Society of Cupconversion of near-infrared photons with nanocrystal light absorbers† Zhiyuan...the energy contained in light in order to improve the performance of photovoltaic devices or photocatalysts.1 Reshaping the solar spectrum to match the...optical properties of common semi- conductors will allow the efficient use of all incident light . While many efforts e.g. hot carrier devices,2

[Multiply upconversion emission in oxyfluoride ceramics].

PubMed

Xiao, Si-guo; Yang, Xiao-liang; Liu, Zhen-wei

2003-02-01

Oxyfluoride ceramics with the host composition of SiO2 and PbF2 have been prepared. X-ray diffraction analysis of the ceramics revealed that fluoride type beta-PbF2 solid solution regions are precipitated in the glass matrix. Rare earth ions in the beta-PbF2 solid solution show highly efficient upconversion performance due to the very small multi-phonon relaxation rates. Eight upconversion emission bands whose central wavelength are 846, 803, 665, 549, 523, 487, 456 and 411 nm have been observed when the sample was excited with 930 nm diode light. Four possible energy transfer processes between Er3+ and Yb3+ cause the electronic population of high energy level of Er3+ and realize the abound upconversion luminescence bands.

A temperature sensor based on the enhanced upconversion luminescence of Li+ doped NaLuF4:Yb3+,Tm3+/Er3+ nano/microcrystals.

PubMed

Qiang, Qinping; Du, Shanshan; Ma, Xinlong; Chen, Wenbo; Zhang, Gangyi; Wang, Yuhua

2018-05-09

In this paper, fluorescent and optical temperature sensing bi-functional Li+-doping NaLuF4:Ln (Ln = Yb3+, Tm3+/Er3+) nanocrystals were synthesized via a simple hydrothermal method using oleic acid as a capping ligand. The crystal phase, size, upconversion (UC) properties, and optical temperature sensing characteristics of the crystals can be easily modified by Li+ doping. The results reveal that additional Li+ can promote the transformation from the hexagonal phase to the cubic phase and reduce the size of the nanocrystals. In addition, NaLuF4:Ln (Ln = Yb3+, Tm3+, Li+) nanocrystals present efficient near infrared (NIR) emission, which is beneficial for in vivo biomedical applications due to the increased penetration depth and low radiation damage of NIR light in bio-tissues. More importantly, under 980 nm excitation, the temperature dependent UCL from the 2H11/2 and 4S3/2 levels of Er3+ ions in NaLuF4:Yb3+,Er3+,Li+ microcrystals was investigated systematically. The fluorescence intensity ratios (FIR) of the pairs of thermally coupled levels were studied as a function of temperature in the range of 298-523 K. The maximum sensor sensitivities were found to be about 0.0039 K-1 (523 K) by exploiting the UC emissions from the 2H11/2 and 4S3/2 levels. This suggests that the Li+-doped upconversion luminescence (UCL) materials are promising prototypes for application as multi-mode probes for use in bio-separation and optical thermometers.

Controllable red, green, blue (RGB) and bright white upconversion luminescence of Lu2O3:Yb3+/Er3+/Tm3+ nanocrystals through single laser excitation at 980 nm.

PubMed

Yang, Jun; Zhang, Cuimiao; Peng, Chong; Li, Chunxia; Wang, Lili; Chai, Ruitao; Lin, Jun

2009-01-01

Light fantastic! Lu(2)O(3):Yb(3+)/Er(3+)/Tm(3+) nanocrystals with controllable red, green, blue (RGB) and bright white upconversion luminescence by a single laser excitation of 980 nm have been successfully synthesized (see picture). Due to abundant UC PL colors, it can potentially be used as fluorophores in the field of color displays, back light, UC lasers, photonics, and biomedicine.Lu(2)O(3):Yb(3+)/Er(3+)/Tm(3+) nanocrystals have been successfully synthesized by a solvothermal process followed by a subsequent heat treatment at 800 degrees C. Powder X-ray diffraction, transmission electron microscopy, upconversion photoluminescence spectra, and kinetic decay were used to characterize the samples. Under single-wavelength diode laser excitation of 980 nm, the bright blue emissions of Lu(2)O(3):Yb(3+), Tm(3+) nanocrystals near 477 and 490 nm were observed due to the (1)G(4)-->(3)H(6) transition of Tm(3+). The bright green UC emissions of Lu(2)O(3):Er(3+) nanocrystals appeared near 540 and 565 nm were observed and assigned to the (2)H(11/2)-->(4)I(15/2) and (4)S(3/2)-->(4)I(15/2) transitions, respectively, of Er(3+). The ratio of the intensity of green luminescence to that of red luminescence decreases with an increase of concentration of Yb(3+) in Lu(2)O(3):Er(3+) nanocrystals. In sufficient quantities of Yb(3+) with resprct to Er(3+), the bright red UC emission of Lu(2)O(3):Yb(3+)/Er(3+) centered at 662 nm was predominant, due to the (4)F(9/2)-->(4)I(15/2) transition of Er(3+). Based on the generation of red, green, and blue emissions in the different doped Lu(2)O(3):RE(3+) nanocrystals, it is possible to produce the luminescence with a wide spectrum of colors, including white, by the appropriate doping of Yb(3+), Tm(3+), and Er(3+) in the present Lu(2)O(3) nanocrystals. Namely, Lu(2)O(3):3 %Yb(3+)/0.2 %Tm(3+)/0.4 %Er(3+) nanocrystals show suitable intensities of blue, green, and red (RGB) emission, resulting in the production of perfect and bright white light with CIE-x=0.3456 and CIE-y=0.3179, which is very close to the standard equal energy white light illuminate (x=0.33, y=0.33). Because of abundant luminescent colors from RGB to white in Lu(2)O(3):Yb(3+)/Er(3+)/Tm(3+) nanocrystals under 980 nm laser diode (LD) excitation, they can potentially be used as fluorophores in the field of color displays, back light, UC lasers, photonics, and biomedicine.

Temperature dependence of the ratio of intensities of up-conversion fluorescence bands of YVO4 and YGdVO4 crystals and lead fluoride nano glass ceramics activated with erbium ions

NASA Astrophysics Data System (ADS)

Varaksa, Yu. A.; Sinitsyn, G. V.; Khodasevich, M. A.; Aseev, V. A.; Kolobkova, E. V.; Yasyukevich, A. S.

2015-01-01

Up-conversion fluorescence spectra of YVO4 and YGdVO4 crystals and lead fluoride nano glass ceramics coactivated with erbium and ytterbium ions have been studied in the wavelength range of 520-560 nm under 967-nm pumping. The ratio of intensities of fluorescence bands in the ranges of 520-530 and 540-550 nm has been measured in the temperature range of from room temperature to 150°C. It is shown that the considered materials can be used for preparing a sensing element of optical fluorescent temperature sensors; the sensitivity of measuring the temperature of nano glass-ceramics can be close to that of crystal samples.

Localized surface plasmons modulated nonlinear optical processes in metal film-coupled and upconversion nanocrystals-coated nanoparticles (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lei, Dangyuan

2016-09-01

In the first part of this talk, I will show our experimental investigation on the linear and nonlinear optical properties of metal film-coupled nanosphere monomers and dimers both with nanometric gaps. We have developed a new methodology - polarization resolved spectral decomposition and color decoding to "visualizing" unambiguously the spectral and radiation properties of the complex plasmonic gap modes in these hybrid nanostructures. Single-particle spectroscopic measurements indicate that these hybrid nanostructures can simultaneously enhance several nonlinear optical processes, such as second harmonic generation, two-photon absorption induced luminescence, and hyper-Raman scattering. In the second part, I will show how the polarization state of the emissions from sub-10 nm upconversion nanocrystals (UCNCs) can be modulated when they form a hybrid complex with a gold nanorod (GNR). Our single-particle scattering experiments expose how an interplay between excitation polarization and GNR orientation gives rise to an extraordinary polarized nature of the upconversion emissions from an individual hybrid nanostructure. We support our results by numerical simulations and, using Förster resonance energy transfer theory, we uncover how an overlap between the UCNC emission and GNR extinction bands as well as the mutual orientation between emission and plasmonic dipoles jointly determine the polarization state of the UC emissions.

The role of Nb in intensity increase of Er ion upconversion luminescence in zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smits, K., E-mail: smits@cfi.lu.lv; Sarakovskis, A.; Grigorjeva, L.

2014-06-07

It is found that Nb co-doping increases the luminescence and upconversion luminescence intensity in rare earth doped zirconia. Er and Yb-doped nanocrystalline samples with or without Nb co-doping were prepared by sol-gel method and thermally annealed to check for the impact of phase transition on luminescence properties. Phase composition and grain sizes were examined by X-ray diffraction; the morphology was checked by scanning- and high-resolution transmission electron microscopes. Both steady-state and time-resolved luminescence were studied. Comparison of samples with different oxygen vacancy concentrations and different Nb concentrations confirmed the known assumption that oxygen vacancies are the main agents for tetragonalmore » or cubic phase stabilization. The oxygen vacancies quench the upconversion luminescence; however, they also prevent agglomeration of rare-earth ions and/or displacement of rare-earth ions to grain surfaces. It is found that co-doping with Nb ions significantly (>20 times) increases upconversion luminescence intensity. Hence, ZrO{sub 2}:Er:Yb:Nb nanocrystals may show promise for upconversion applications.« less

Methods and compositions for the upconversion of light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baldo, Marc A.; Congreve, Daniel N.; Thompson, Nicholas John

The present invention generally relates to composition and methods for upconverting light. In some embodiments, the composition and methods comprise an organic material, a nanocrystal, and a ligand capable of facilitating energy transfer between the nanocrystal and the organic material. In certain embodiments, the nanocrystal has a first excited energy state with an energy greater than a triplet state of the organic material. The organic material, in some embodiments, may be aromatic and/or include one or more pi-conjugated carbon-carbon double bonds. In some cases, incident light may be absorbed by the nanocrystal to produce triplet excitons. The triplet excitons maymore » then transfer from the nanocrystal to the organic material and undergo triplet-triplet annihilation, creating a singlet state of approximately twice the energy of the triplet exciton. In certain embodiments, the singlet state fluoresces, resulting in the formation of a high energy photon.« less

Amelogenin-assisted ex vivo remineralization of human enamel: effects of supersaturation degree and fluoride concentration

PubMed Central

Fan, Yuwei; Nelson, James R.; Alvarez, Jason R.; Hagan, Joseph; Berrier, Allison; Xu, Xiaoming

2011-01-01

The formation of organized nanocrystals that resemble enamel is crucial for successful enamel remineralization. Calcium, phosphate and fluoride ions and amelogenin are important ingredients for the formation of organized hydroxyapatite (HAP) crystals in vitro. However, the effects of these remineralization agents on the enamel crystal morphology have not been thoroughly studied. The objective of this study was to investigate the effects of fluoride ions, supersaturation degree and amelogenin on the crystal morphology and organization of ex vivo remineralized human enamel. Extracted third molars were sliced thin and acid-etched to provide the enamel surface for immersion in different remineralization solutions. The crystal morphology and mineral phase of the remineralized enamel surface were analyzed by FE-SEM, ATR-FTIR and XRD. The concentration of fluoride and supersaturation degree of hydroxyapatite had significant effects on the crystal morphology and crystal organization, which varied from plate-like loose crystals to rod-like densely packed nanocrystal arrays. Densely packed arrays of fluoridated hydroxyapatite nanorods were observed under the following conditions: σ(HAP) = 10.2±2.0 with fluoride 1.5±0.5 mg/L and amelogenin 40±10 µg/mL, pH 6.8±0.4. A phase diagram summarized the conditions that form dense or loose hydroxyapatite nanocrystal structures. This study provides the basis for the development of novel dental materials for caries management. PMID:21256987

Upconversion microparticles as time-resolved luminescent probes for multiphoton microscopy: desired signal extraction from the streaking effect

NASA Astrophysics Data System (ADS)

Pominova, Daria V.; Ryabova, Anastasia V.; Grachev, Pavel V.; Romanishkin, Igor D.; Kuznetsov, Sergei V.; Rozhnova, Julia A.; Yasyrkina, Daria S.; Fedorov, Pavel P.; Loschenov, Victor B.

2016-09-01

The great interest in upconversion nanoparticles exists due to their high efficiency under multiphoton excitation. However, when these particles are used in scanning microscopy, the upconversion luminescence causes a streaking effect due to the long lifetime. This article describes a method of upconversion microparticle luminescence lifetime determination with help of modified Lucy-Richardson deconvolution of laser scanning microscope (LSM) image obtained under near-IR excitation using nondescanned detectors. Determination of the upconversion luminescence intensity and the decay time of separate microparticles was done by intensity profile along the image fast scan axis approximation. We studied upconversion submicroparticles based on fluoride hosts doped with Yb3+-Er3+ and Yb3+-Tm3+ rare earth ion pairs, and the characteristic decay times were 0.1 to 1.5 ms. We also compared the results of LSM measurements with the photon counting method results; the spread of values was about 13% and was associated with the approximation error. Data obtained from live cells showed the possibility of distinguishing the position of upconversion submicroparticles inside and outside the cells by the difference of their lifetime. The proposed technique allows using the upconversion microparticles without shells as probes for the presence of OH- ions and CO2 molecules.

Enhanced Upconversion Luminescence in Yb3+/Tm3+-Codoped Fluoride Active Core/Active Shell/Inert Shell Nanoparticles through Directed Energy Migration.

PubMed

Qiu, Hailong; Yang, Chunhui; Shao, Wei; Damasco, Jossana; Wang, Xianliang; Ågren, Hans; Prasad, Paras N; Chen, Guanying

2014-01-03

The luminescence efficiency of lanthanide-doped upconversion nanoparticles is of particular importance for their embodiment in biophotonic and photonic applications. Here, we show that the upconversion luminescence of typically used NaYF₄:Yb 3+ 30%/Tm 3+ 0.5% nanoparticles can be enhanced by ~240 times through a hierarchical active core/active shell/inert shell (NaYF₄:Yb 3+ 30%/Tm 3+ 0.5%)/NaYbF₄/NaYF₄ design, which involves the use of directed energy migration in the second active shell layer. The resulting active core/active shell/inert shell nanoparticles are determined to be about 11 times brighter than that of well-investigated (NaYF₄:Yb 3+ 30%/Tm 3+ 0.5%)/NaYF₄ active core/inert shell nanoparticles when excited at ~980 nm. The strategy for enhanced upconversion in Yb 3+ /Tm 3+ -codoped NaYF₄ nanoparticles through directed energy migration might have implications for other types of lanthanide-doped upconversion nanoparticles.

In-situ second harmonic generation by cancer cell targeting ZnO nanocrystals to effect photodynamic action in subcellular space.

PubMed

Gu, Bobo; Pliss, Artem; Kuzmin, Andrey N; Baev, Alexander; Ohulchanskyy, Tymish Y; Damasco, Jossana A; Yong, Ken-Tye; Wen, Shuangchun; Prasad, Paras N

2016-10-01

This paper introduces the concept of in-situ upconversion of deep penetrating near infrared light via second harmonic generation from ZnO nanocrystals delivered into cells to effect photo activated therapies, such as photodynamic therapy, which usually require activation by visible light with limited penetration through biological tissues. We demonstrated this concept by subcellular activation of a photodynamic therapy drug, Chlorin e6, excited within its strong absorption Soret band by the second harmonic (SH) light, generated at 409 nm by ZnO nanocrystals, which were targeted to cancer cells and internalized through the folate-receptor mediated endocytosis. By a combination of theoretical modeling and experimental measurements, we show that SH light, generated in-situ by ZnO nanocrystals significantly contributes to activation of photosensitizer, leading to cell death through both apoptotic and necrotic pathways initiated in the cytoplasm. This targeted photodynamic action was studied using label-free Coherent Anti-Stokes Raman Scattering imaging of the treated cells to monitor changes in the distribution of native cellular proteins and lipids. We found that initiation of photodynamic therapy with upconverted light led to global reduction in the intracellular concentration of macromolecules, likely due to suppression of proteins and lipids synthesis, which could be considered as a real-time indicator of cellular damage from photodynamic treatment. In prospective applications this in-situ photon upconversion could be further extended using ZnO nanocrystals surface functionalized with a specific organelle targeting group, provided a powerful approach to identify and consequently maximize a cellular response to phototherapy, selectively initiated in a specific cellular organelle. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis and up-conversion luminescence of Er{sup 3+} and Y b{sup 3+} codoped nanocrystalline tetra- (KLaP{sub 4}O{sub 12}) and pentaphosphates (LaP{sub 5}O{sub 14})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marciniak, L., E-mail: l.marciniak@int.pan.wroc.pl; Stefanski, M.; Tomala, R.

2015-09-07

The up-converting nanocrystals of KLa{sub 0.95}Er{sub 0.05}Y b{sub x}P{sub 4}O{sub 12} and La{sub 0.95−x}Er{sub 0.05}Y b{sub x}P{sub 5}O{sub 14} were prepared using co-precipitation method. The spectroscopic properties of these materials were investigated in a function of Y b{sup 3+} concentration. The up-conversion emission, power dependence of emission intensities, and the luminescence decay times were investigated. It was found that the green to red and {sup 2}H{sub 11/2} → {sup 4}I{sub 15/2} to {sup 4}S{sub 3/2} → {sup 4}I{sub 15/2} emission intensity ratio were strongly affected by the Y b{sup 3+} concentration. Moreover, the order of up-conversion emission and threshold powermore » rises up with Y b{sup 3+} concentration for {sup 4}S{sub 3/2} → {sup 4}I{sub 15/2} transition. The luminescence decay time of the {sup 4}S{sub 3/2} → {sup 4}I{sub 15/2} emission increases with Y b{sup 3+} concentration while the {sup 4}F{sub 9/2} → {sup 4}I{sub 15/2} emission is independent of dopant concentration. The influence of the Y b{sup 3+} concentration on the up-conversion emission intensities was discussed in terms of concentration dependent hetero looped photon avalanche process. A comparison of the up-conversion properties of KLa{sub 0.95}Er{sub 0.05}Y b{sub x}P{sub 4}O{sub 12} and La{sub 0.95−x}Er{sub 0.05}Y b{sub x}P{sub 5}O{sub 14} nanocrystals was presented.« less

A dual-targeting upconversion nanoplatform for two-color fluorescence imaging-guided photodynamic therapy.

PubMed

Wang, Xu; Yang, Cheng-Xiong; Chen, Jia-Tong; Yan, Xiu-Ping

2014-04-01

The targetability of a theranostic probe is one of the keys to assuring its theranostic efficiency. Here we show the design and fabrication of a dual-targeting upconversion nanoplatform for two-color fluorescence imaging-guided photodynamic therapy (PDT). The nanoplatform was prepared from 3-aminophenylboronic acid functionalized upconversion nanocrystals (APBA-UCNPs) and hyaluronated fullerene (HAC60) via a specific diol-borate condensation. The two specific ligands of aminophenylboronic acid and hyaluronic acid provide synergistic targeting effects, high targetability, and hence a dramatically elevated uptake of the nanoplatform by cancer cells. The high generation yield of (1)O2 due to multiplexed Förster resonance energy transfer between APBA-UCNPs (donor) and HAC60 (acceptor) allows effective therapy. The present nanoplatform shows great potential for highly selective tumor-targeted imaging-guided PDT.

3D assembly of upconverting NaYF4 nanocrystals by AFM nanoxerography: creation of anti-counterfeiting microtags

NASA Astrophysics Data System (ADS)

Sangeetha, Neralagatta M.; Moutet, Pierre; Lagarde, Delphine; Sallen, Gregory; Urbaszek, Bernhard; Marie, Xavier; Viau, Guillaume; Ressier, Laurence

2013-09-01

Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags.Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags. Electronic supplementary information (ESI) available: Detailed experimental procedures for the synthesis of upconverting NaYF4 nanocrystals and their transmission electron microscopy images. KFM and AFM images corresponding to the assembly of positively charged β-NaYF4:Er3+,Yb3+ nanocrystals from water suspensions by AFM nanoxerography. Photoluminescence spectra of β-NaYF4:Er3+,Yb3+ nanocrystals in a hexane suspension and assembled on charge patterns. See DOI: 10.1039/c3nr02734a

Diffusion and aggregation of subsurface radiation defects in lithium fluoride nanocrystals

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Martynovich, E. F.; Stupak, A. P.; Runets, L. P.

2015-09-01

Lithium fluoride nanocrystals were irradiated by gamma rays at a temperature below the temperature corresponding to the mobility of anion vacancies. The kinetics of the aggregation of radiation-induced defects in subsurface layers of nanocrystals during annealing after irradiation was elucidated. The processes that could be used to determine the activation energy of the diffusion of anion vacancies were revealed. The value of this energy in subsurface layers was obtained. For subsurface layers, the concentrations ratio of vacancies and defects consisting of one vacancy and two electrons was found. The factors responsible for the differences in the values of the activation energies and concentration ratios in subsurface layers and in the bulk of the crystals were discussed.

Enhanced Upconversion Luminescence in Yb3+/Tm3+-Codoped Fluoride Active Core/Active Shell/Inert Shell Nanoparticles through Directed Energy Migration

PubMed Central

Qiu, Hailong; Yang, Chunhui; Shao, Wei; Damasco, Jossana; Wang, Xianliang; Ågren, Hans; Prasad, Paras N.; Chen, Guanying

2014-01-01

The luminescence efficiency of lanthanide-doped upconversion nanoparticles is of particular importance for their embodiment in biophotonic and photonic applications. Here, we show that the upconversion luminescence of typically used NaYF4:Yb3+30%/Tm3+0.5% nanoparticles can be enhanced by ~240 times through a hierarchical active core/active shell/inert shell (NaYF4:Yb3+30%/Tm3+0.5%)/NaYbF4/NaYF4 design, which involves the use of directed energy migration in the second active shell layer. The resulting active core/active shell/inert shell nanoparticles are determined to be about 11 times brighter than that of well-investigated (NaYF4:Yb3+30%/Tm3+0.5%)/NaYF4 active core/inert shell nanoparticles when excited at ~980 nm. The strategy for enhanced upconversion in Yb3+/Tm3+-codoped NaYF4 nanoparticles through directed energy migration might have implications for other types of lanthanide-doped upconversion nanoparticles. PMID:28348285

Shape-Controlled Synthesis of Isotopic Yttrium-90-Labeled Rare Earth Fluoride Nanocrystals for Multimodal Imaging.

PubMed

Paik, Taejong; Chacko, Ann-Marie; Mikitsh, John L; Friedberg, Joseph S; Pryma, Daniel A; Murray, Christopher B

2015-09-22

Isotopically labeled nanomaterials have recently attracted much attention in biomedical research, environmental health studies, and clinical medicine because radioactive probes allow the elucidation of in vitro and in vivo cellular transport mechanisms, as well as the unambiguous distribution and localization of nanomaterials in vivo. In addition, nanocrystal-based inorganic materials have a unique capability of customizing size, shape, and composition; with the potential to be designed as multimodal imaging probes. Size and shape of nanocrystals can directly influence interactions with biological systems, hence it is important to develop synthetic methods to design radiolabeled nanocrystals with precise control of size and shape. Here, we report size- and shape-controlled synthesis of rare earth fluoride nanocrystals doped with the β-emitting radioisotope yttrium-90 ((90)Y). Size and shape of nanocrystals are tailored via tight control of reaction parameters and the type of rare earth hosts (e.g., Gd or Y) employed. Radiolabeled nanocrystals are synthesized in high radiochemical yield and purity as well as excellent radiolabel stability in the face of surface modification with different polymeric ligands. We demonstrate the Cerenkov radioluminescence imaging and magnetic resonance imaging capabilities of (90)Y-doped GdF3 nanoplates, which offer unique opportunities as a promising platform for multimodal imaging and targeted therapy.

Labeling of HeLa cells using ZrO2:Yb3+-Er3+ nanoparticles with upconversion emission

NASA Astrophysics Data System (ADS)

Ceja-Fdez, Andrea; López-Luke, Tzarara; Oliva, Jorge; Vivero-Escoto, Juan; Gonzalez-Yebra, Ana Lilia; Rojas, Ruben A. Rodriguez; Martínez-Pérez, Andrea; de la Rosa, Elder

2015-04-01

This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2-1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.

Application of upconversion luminescent-magnetic microbeads with weak background noise and facile separation in ochratoxin A detection

NASA Astrophysics Data System (ADS)

Liao, Zhenyu; Zhang, Ying; Su, Lin; Chang, Jin; Wang, Hanjie

2017-02-01

Ochratoxin A (OTA), the most harmful and abundant ochratoxin, is chemically stable and commonly existed in foodstuffs. In this work, upconversion luminescent-magnetic microbeads (UCLMMs) -based cytometric bead array for OTA detection with a less reagent consumption and high sensitivity has been established and optimized. In UCLMMs, upconversion nanocrystals (UCNs) for optical code present a weak background noise and no spectral cross talk between the encoding signals and target labels under two excitation conditions to improve detection sensitivity. While the superparamagnetic Fe3O4 nanoparticles (Fe3O4 NPs) aim for rapid analysis. The results show that the developed method has a sensitivity of 9.553 ppt below HPLC with a 50-μL sample and can be completed in <2 h with good accuracy and high reproducibility. Therefore, different colors of UCLMMs will become a promising assay platform for multiple mycotoxins after further improvement.

Effect of the CTAB concentration on the upconversion emission of ZrO 2:Er 3+ nanocrystals

NASA Astrophysics Data System (ADS)

López-Luke, T.; De la Rosa, E.; Sólis, D.; Salas, P.; Angeles-Chavez, C.; Montoya, A.; Díaz-Torres, L. A.; Bribiesca, S.

2006-10-01

Upconversion emission of ZrO 2:Er 3+ (0.2 mol%) nanophosphor were studied as function of surfactant concentration after excitation at 968 nm. The strong green emission was produced by the transition 2H 11/2 + 4S 3/2 → 4I 15/2 and was explained in terms of cooperative energy transfer between neighboring ions. The upconverted signal was enhanced but the fluorescence decay time was reduced as either the surfactant concentration increases or the annealing time reduces. Experimental results show that surfactant concentration controls the particle size and morphology while annealing time control the phase composition and crystallite size. The highest intensity was obtained for a sample composed of a mixture of tetragonal (33 wt.%) and monoclinic (67 wt.%) phase with crystallite size of 31 and 59 nm, respectively. This result suggests that tetragonal crystalline structure and small crystallite size are more favorable for the upconversion emission.

Photocatalytic Water-Splitting Enhancement by Sub-Bandgap Photon Harvesting.

PubMed

Monguzzi, Angelo; Oertel, Amadeus; Braga, Daniele; Riedinger, Andreas; Kim, David K; Knüsel, Philippe N; Bianchi, Alberto; Mauri, Michele; Simonutti, Roberto; Norris, David J; Meinardi, Francesco

2017-11-22

Upconversion is a photon-management process especially suited to water-splitting cells that exploit wide-bandgap photocatalysts. Currently, such catalysts cannot utilize 95% of the available solar photons. We demonstrate here that the energy-conversion yield for a standard photocatalytic water-splitting device can be enhanced under solar irradiance by using a low-power upconversion system that recovers part of the unutilized incident sub-bandgap photons. The upconverter is based on a sensitized triplet-triplet annihilation mechanism (sTTA-UC) obtained in a dye-doped elastomer and boosted by a fluorescent nanocrystal/polymer composite that allows for broadband light harvesting. The complementary and tailored optical properties of these materials enable efficient upconversion at subsolar irradiance, allowing the realization of the first prototype water-splitting cell assisted by solid-state upconversion. In our proof-of concept device the increase of the performance is 3.5%, which grows to 6.3% if concentrated sunlight (10 sun) is used. Our experiments show how the sTTA-UC materials can be successfully implemented in technologically relevant devices while matching the strict requirements of clean-energy production.

Visible upconversion emission and non-radiative direct Yb 3+ to Er 3+ energy transfer processes in nanocrystalline ZrO 2:Yb 3+,Er 3+

NASA Astrophysics Data System (ADS)

Diaz-Torres, L. A.; Meza, O.; Solis, D.; Salas, P.; De la Rosa, E.

2011-06-01

Wide band gap Yb 3+ and Er 3+ codoped ZrO 2 nanocrystals have been synthesized by a modified sol-gel method. Under 967 nm excitation strong green and red upconversion emission is observed for several Er 3+ to Yb 3+ ions concentration ratios. A simple microscopic rate equation model is used to study the effects of non-radiative direct Yb 3+ to Er 3+ energy transfer processes on the visible and near infrared fluorescence decay trends of both Er 3+ and Yb 3+ ions. The microscopic rate equation model takes into account the crystalline phase as well as the size of nanocrystals. Nanocrystals phase and size were estimated from XRD patterns. The rate equation model succeeds to fit simultaneously all visible and near infrared fluorescence decay profiles. The dipole-dipole interaction parameters that drive the non-radiative energy transfer processes depend on doping concentration due to crystallite phase changes. In addition the non-radiative relaxation rate ( 4I11/2→ 4I13/2) is found to be greater than that estimated by the Judd-Ofelt parameters due to the action of surface impurities. Results suggest that non-radiative direct Yb 3+ to Er 3+ energy transfer processes in ZrO 2:Yb,Er are extremely efficient.

Visible-to-visible four-photon ultrahigh resolution microscopic imaging with 730-nm diode laser excited nanocrystals.

PubMed

Wang, Baoju; Zhan, Qiuqiang; Zhao, Yuxiang; Wu, Ruitao; Liu, Jing; He, Sailing

2016-01-25

Further development of multiphoton microscopic imaging is confronted with a number of limitations, including high-cost, high complexity and relatively low spatial resolution due to the long excitation wavelength. To overcome these problems, for the first time, we propose visible-to-visible four-photon ultrahigh resolution microscopic imaging by using a common cost-effective 730-nm laser diode to excite the prepared Nd(3+)-sensitized upconversion nanoparticles (Nd(3+)-UCNPs). An ordinary multiphoton scanning microscope system was built using a visible CW diode laser and the lateral imaging resolution as high as 161-nm was achieved via the four-photon upconversion process. The demonstrated large saturation excitation power for Nd(3+)-UCNPs would be more practical and facilitate the four-photon imaging in the application. A sample with fine structure was imaged to demonstrate the advantages of visible-to-visible four-photon ultrahigh resolution microscopic imaging with 730-nm diode laser excited nanocrystals. Combining the uniqueness of UCNPs, the proposed visible-to-visible four-photon imaging would be highly promising and attractive in the field of multiphoton imaging.

Interference-enhanced infrared-to-visible upconversion in solid-state thin films sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Jean, Joel; Bulović, Vladimir; Baldo, Marc A.

2017-05-01

Infrared-to-visible photon upconversion has potential applications in photovoltaics, sensing, and bioimaging. We demonstrate a solid-state thin-film device that utilizes sensitized triplet-triplet exciton annihilation, converting infrared photons absorbed by colloidal lead sulfide nanocrystals (NCs) into visible photons emitted from a luminescent dopant in rubrene at low incident light intensities. A typical bilayer device consisting of a monolayer of NCs and a doped film of rubrene is limited by low infrared absorption in the thin NC film. Here, we augment the bilayer with an optical spacer layer and a silver-film back reflector, resulting in interference effects that enhance the optical field and thus the absorption in the NC film. The interference-enhanced device shows an order-of-magnitude increase in the upconverted emission at the wavelength of λ = 610 nm when excited at λ = 980 nm. At incident light intensities above 1.1 W/cm2, the device attains maximum efficiency, converting (1.6 ± 0.2)% of absorbed infrared photons into higher-energy singlet excitons in rubrene.

Cubic sub-20 nm NaLuF(4)-based upconversion nanophosphors for high-contrast bioimaging in different animal species.

PubMed

Yang, Tianshe; Sun, Yun; Liu, Qian; Feng, Wei; Yang, Pengyuan; Li, Fuyou

2012-05-01

A new upconversion luminescence (UCL) nanophosphors based on host matrix of cubic NaLuF(4) with bright luminescence have been synthesized by a solvothermal method, facilitate the nanocrystals potential candidates for imaging in vivo, especially large-animals. The sub-20 nm NaLuF(4) co-doped Yb(3+) and Er(3+) (Tm(3+)) showed about 10-fold stronger UCL emission than that of corresponding hexagonal NaYF(4)-based nanocrystals with a 20 nm diameter. Near-infrared to near-infrared (NIR-to-NIR) UCL emission of PAA-coated NaLuF(4):20%Yb,1%Tm (PAA-Lu(Tm)) can penetrate >1.5 cm tissue of pork with high contrast. Based on super-strong UCL emission and deep penetration, PAA-Lu(Tm) as optical bioprobe has been demonstrated by in vivo UCL imaging of a normal black mouse, even rabbit with excellent signal-to-noise ratio. Furthermore, such cubic NaLuF(4)-based nanophosphor was applied in lymph node imaging of live Kunming mouse with rich white fur. Copyright © 2012 Elsevier Ltd. All rights reserved.

Structural and luminescent properties of a NaYF4-aerogel composite

NASA Astrophysics Data System (ADS)

Alattar, Ashraf M.; Drexler, Matthew; Twej, Wesam A. A.; Alamgir, Faisal M.

2018-07-01

Upconversion materials, capable of energy-shifting light, have direct application in devices where the tunability of the optical spectrum can result in higher performance. Due to the low transparency of upconversion nanomaterials, it is beneficial to disperse them in a medium with a low optical attenuation coefficient in order to allow light to reach and increase the contributions from each individual particle. Silica aerogels, with their high transparency and open porosity, are ideal media for the dispersion of the nanomaterials throughout a volume. NaYF4-based nanocrystals with differing dopants were incorporated into silica xerogels and aerogels to observe the effect of the composites on the properties of each. It was observed that, while the average surface area of the aerogel decreased in the composite, the shape and phase of the nanocrystals were preserved during xerogel processing. The luminescence of the nanoparticles increased upon incorporation into the xerogel composites. By accounting for effects emerging from collection geometry and the composite morphology, it is argued that the increase in the composite luminescent intensity is due to the nanoparticles being shielded from quenching effects by the silica matrix.

Photon up-conversion production in Tb{sup 3+}–Yb{sup 3+} co-doped CaF{sub 2} phosphors prepared by combustion synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rakov, Nikifor, E-mail: nikifor.gomez@univasf.edu.br; Guimarães, Renato B.; Maciel, Glauco S., E-mail: glauco@if.uff.br

2016-02-15

Graphical abstract: Up-conversion luminescence from Tb{sup 3+} obtained by energy transfer from Yb{sup 3+} pairs in CaF{sub 2} powder prepared by combustion synthesis. - Highlights: • Calcium fluoride (CaF{sub 2}) powders were prepared by combustion synthesis. • Rare-earth ions doped in this material were found in interstitial sites. • Cooperative up-conversion was observed in Tb{sup 3+}:Yb{sup 3+}:CaF{sub 2} powder. • Energy transfer between Tb{sup 3+} and pairs of Yb{sup 3+} was analyzed using rate equations. - Abstract: Calcium fluoride (CaF{sub 2}) crystalline powders were successfully prepared by the combustion synthesis method. The powder material containing luminescent rare-earth ions, more specificallymore » terbium (Tb{sup 3+}) and ytterbium (Yb{sup 3+}), was studied by X-ray diffraction, scanning electronic microscopy and optical spectroscopy. These ions are allocated in charge compensated interstitial positions of tetragonal (C{sub 4v}) and trigonal (C{sub 3v}) symmetry sites of the cubic (O{sub h}) CaF{sub 2} lattice. Up-conversion (UC) luminescence in Tb{sup 3+} was achieved using a low power diode laser operating at 975 nm. Tb{sup 3+} is insensitive to near-infrared radiation but UC can be achieved via energy transfer from pairs of Yb{sup 3+} ions to Tb{sup 3+} ions. The UC luminescence dynamics of Tb{sup 3+} was used to study the energy transfer mechanism.« less

Magnetic and upconverted luminescent properties of multifunctional lanthanide doped cubic KGdF4 nanocrystals.

PubMed

Yang, L W; Zhang, Y Y; Li, J J; Li, Y; Zhong, J X; Chu, Paul K

2010-12-01

Lanthanide (Ln3+) doped KGdF4 (Ln=Yb3+, Er3+, Ho3+, Tm3+) nanocrystals with a mean diameter of approximately 12 nm were synthesized by a hydrothermal method using oleic acid as a stabilizing agent at 180 °C. The nanocrystals crystallize in the cubic phase as α-NaGdF4. When excited by a 980 nm laser, these Ln3+ doped nanocrystals exhibit multicolor up-conversion (UC) emissions in red, yellow, blue and white. The calculated color coordinates demonstrate that white UC emission (CIE-X=0.352, CIE-Y=0.347) can be obtained by varying the dopant concentrations in the Yb3+/Ho3+/Tm3+ triply-doped nanocrystals to yield different RGB emission intensities. The measured field dependence of magnetization (M-H curves) of the KGdF4 nanocrystals shows their paramagnetic characteristics that can be ascribed to the non-interacting localized nature of the magnetic moment of Gd3+ ions. Moreover, low temperature thermal treatment can enhance UC properties, magnetization and magnetic mass susceptibility of Ln3+ doped KGdF4 nanocrystals. The multifunctional Ln3+ doped KGdF4 nanocrystals have potential applications in color displays, bioseparation, and optical-magnetic dual modal nanoprobes in biomedical imaging.

Magnetic and upconverted luminescent properties of multifunctional lanthanide doped cubic KGdF4nanocrystals

NASA Astrophysics Data System (ADS)

Yang, L. W.; Zhang, Y. Y.; Li, J. J.; Li, Y.; Zhong, J. X.; Chu, Paul K.

2010-12-01

Lanthanide (Ln3+) doped KGdF4 (Ln = Yb3+, Er3+, Ho3+, Tm3+) nanocrystals with a mean diameter of approximately 12 nm were synthesized by a hydrothermal method using oleic acid as a stabilizing agent at 180 °C. The nanocrystals crystallize in the cubic phase as α-NaGdF4. When excited by a 980 nm laser, these Ln3+ doped nanocrystals exhibit multicolor up-conversion (UC) emissions in red, yellow, blue and white. The calculated color coordinates demonstrate that white UC emission (CIE-X = 0.352, CIE-Y = 0.347) can be obtained by varying the dopant concentrations in the Yb3+/Ho3+/Tm3+ triply-doped nanocrystals to yield different RGB emission intensities. The measured field dependence of magnetization (M-H curves) of the KGdF4nanocrystals shows their paramagnetic characteristics that can be ascribed to the non-interacting localized nature of the magnetic moment of Gd3+ ions. Moreover, low temperature thermal treatment can enhance UC properties, magnetization and magnetic mass susceptibility of Ln3+ doped KGdF4nanocrystals. The multifunctional Ln3+ doped KGdF4nanocrystals have potential applications in color displays, bioseparation, and optical-magnetic dual modal nanoprobes in biomedical imaging.

Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals.

PubMed

Grzyb, Tomasz; Runowski, Marcin; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2013-01-01

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF 3 @CeF 3 and TbF 3 @CeF 3 @SiO 2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO 2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF 3 @CeF 3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, 'the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb 3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO 2 shell. .

Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Grzyb, Tomasz; Runowski, Marcin; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2013-10-01

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF3@CeF3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, `the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO2 shell.

Energy transfer and up-conversion in rare-earth doped dielectric crystals

NASA Astrophysics Data System (ADS)

Tkachuk, Alexandra M.

1996-01-01

In this work, we consider the prospects of development of the visible, and IR laser-diode pumped lasers based on TR3+-doped double-fluoride crystals. On the basis of estimates of the probabilities of competing non-radiative energy-transfer processes obtained from the experiments and theoretical calculations, the conclusions are drawn on the efficiency of up-conversion pumping and selfquenching of the upper TR3+ states excited by laser-diode emission. The effect of the host composition, dopant concentration, and temperature on the efficiency of up-conversion processes is demonstrated on the example of the YLF:Nd, YLF:Er, BaY2F8:Er, and BaY2F8:Er,Yb crystals. The transfer microparameters for most important cross-relaxation transitions are determined and the conclusions about interaction mechanisms are drawn.

Synthesis of optimized indium phosphide/zinc sulfide core/shell nanocrystals and titanium dioxide nanotubes for quantum dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Lee, Seungyong

Synthesis of InP/ZnS core/shell nanocrystals and TiO 2 nanotubes and the optimization study to couple them together were explored for quantum dot sensitized solar cells. Its intrinsic nontoxicity makes the direct band gap InP/ZnS core/shell be one of the most promising semiconductor nanocrystals for optoelectric applications, with the advantage of tuning the optical absorption range in the desired solar spectrum region. Highly luminescent and monodisperse InP/ZnS nanocrystals were synthesized in a non-coordinating solvent. By varying the synthesis scheme, different size InP/ZnS nanocrystals with emission peaks ranging from 520 nm to 620 nm were grown. For the purpose of ensuring air stability, a ZnS shell was grown. The ZnS shell improves the chemical stability in terms of oxidation prevention. Transmission electron microscopy (TEM) image shows that the nanocrystals are highly crystalline and monodisperse. Free-standing TiO2 nanotubes were produced by an anodization method using ammonium fluoride. The free-standing nanotubes were formed under the condition that the chemical dissolution speed associated with fluoride concentration was faster than the speed of Ti oxidation. Highly ordered free-standing anatase form TiO2 nanotubes, which are transformed by annealing at the optimized temperature, are expected to be ideal for coupling with the prepared InP/ZnS nanocrystals. Electrophoretic deposition was carried out to couple the InP/ZnS nanocrystals with the TiO2 nanotubes. Under the adjusted applied voltage condition, the current during the electrophoretic deposition decreased continuously with time. The amount of the deposited nanocrystals was estimated by calculation and the evenly deposited nanocrystals on the TiO2 nanotubes were observed by TEM.

Upconverting core-shell nanocrystals with high quantum yield under low irradiance: On the role of isotropic and thick shells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fischer, Stefan; Goldschmidt, Jan Christoph; Johnson, Noah J. J.

2015-11-21

Colloidal upconverter nanocrystals (UCNCs) that convert near-infrared photons to higher energies are promising for applications ranging from life sciences to solar energy harvesting. However, practical applications of UCNCs are hindered by their low upconversion quantum yield (UCQY) and the high irradiances necessary to produce relevant upconversion luminescence. Achieving high UCQY under practically relevant irradiance remains a major challenge. The UCQY is severely limited due to non-radiative surface quenching processes. We present a rate equation model for migration of the excitation energy to show that surface quenching does not only affect the lanthanide ions directly at the surface but also manymore » other lanthanide ions quite far away from the surface. The average migration path length is on the order of several nanometers and depends on the doping as well as the irradiance of the excitation. Using Er{sup 3+}-doped β-NaYF{sub 4} UCNCs, we show that very isotropic and thick (∼10 nm) β-NaLuF{sub 4} inert shells dramatically reduce the surface-related quenching processes, resulting in much brighter upconversion luminescence at simultaneously considerably lower irradiances. For these UCNCs embedded in poly(methyl methacrylate), we determined an internal UCQY of 2.0% ± 0.2% using an irradiance of only 0.43 ± 0.03 W/cm{sup 2} at 1523 nm. Normalized to the irradiance, this UCQY is 120× higher than the highest values of comparable nanomaterials in the literature. Our findings demonstrate the important role of isotropic and thick shells in achieving high UCQY at low irradiances from UCNCs. Additionally, we measured the additional short-circuit current due to upconversion in silicon solar cell devices as a proof of concept and to support our findings determined using optical measurements.« less

Controllable optical modulation of blue/green up-conversion fluorescence from Tm3+ (Er3+) single-doped glass ceramics upon two-step excitation of two-wavelengths

PubMed Central

Chen, Zhi; Kang, Shiliang; Zhang, Hang; Wang, Ting; Lv, Shichao; Chen, Qiuqun; Dong, Guoping; Qiu, Jianrong

2017-01-01

Optical modulation is a crucial operation in photonics for network data processing with the aim to overcome information bottleneck in terms of speed, energy consumption, dispersion and cross-talking from conventional electronic interconnection approach. However, due to the weak interactions between photons, a facile physical approach is required to efficiently manipulate photon-photon interactions. Herein, we demonstrate that transparent glass ceramics containing LaF3: Tm3+ (Er3+) nanocrystals can enable fast-slow optical modulation of blue/green up-conversion fluorescence upon two-step excitation of two-wavelengths at telecom windows (0.8–1.8 μm). We show an optical modulation of more than 1500% (800%) of the green (blue) up-conversion fluorescence intensity, and fast response of 280 μs (367 μs) as well as slow response of 5.82 ms (618 μs) in the green (blue) up-conversion fluorescence signal, respectively. The success of manipulating laser at telecom windows for fast-slow optical modulation from rear-earth single-doped glass ceramics may find application in all-optical fiber telecommunication areas. PMID:28368041

Optical thermometry based on green upconversion emission in Er3+/Yb3+ codoped BaGdF5 glass ceramics

NASA Astrophysics Data System (ADS)

Wu, Ting; Zhao, Shilong; Lei, Ruoshan; Huang, Lihui; Xu, Shiqing

2018-02-01

Er3+/Yb3+ codoped BaGdF5 glass ceramics have been prepared and used to develop a portable all-fiber temperature sensor based on fluorescence intensity ratio technique. XRD and TEM results affirm the generation of BaGdF5 nanocrystals in the borosilicate glass. Eu3+ ions are used as spectral probe to investigate external environment around rare earth (RE) ions. Intense green upconversion emissions from Er3+ ions are detected in the BaGdF5 glass ceramics and their intensity are enhanced about three orders of magnitude after heat treatment, which is attributed to the enrichment of RE ions in the BaGdF5 phase. Based on green upconversion emission from Er3+ ions, the temperature sensing property of the portable all-fiber temperature sensor is studied. The maximum absolute sensitivity is 15.5 × 10-4 K-1 at 567 K and the relative sensitivity is 1.28% K-1 at 298 K, respectively.

Up-conversion green emission of Yb3+/Er3+ ions doped YVO4 nanocrystals obtained via modified Pechini's method

NASA Astrophysics Data System (ADS)

Szczeszak, Agata; Runowski, Marcin; Wiglusz, Rafal J.; Grzyb, Tomasz; Lis, Stefan

2017-12-01

A series of lanthanide doped yttrium vanadates were prepared by Pechini's method (sol-gel process). The as-prepared precursors, in the presence of citric acid, were calcined in the temperature range of 600-900 °C. The obtained products were composed of small nanoparticles, in the size range of 20-50 nm, depending on the annealing temperature, exhibiting a bright green up-conversion emission, under NIR laser irradiation, and emission lifetimes in the range of 4.7-18.3 μs. Their structural, morphological and spectroscopic properties were investigated in detail by XRD, HR-TEM including FFT analysis, EDX and spectroscopic techniques (emission, power dependence and emission kinetics). The luminescence quenching phenomenon, manifested in a decrease of up-conversion intensity and shortening of emission lifetime, was observed with increasing of the Yb3+ ion concentration and decreasing the particle size. The optimal concentration of the Yb3+ ions was found to be 15 mol% (YVO4: Yb3+ 15 mol%, Er3+ 2 mol%).

Engineering Plasmonic Nanocrystal Coupling through Template-Assisted Self-Assembly

NASA Astrophysics Data System (ADS)

Greybush, Nicholas J.

The construction of materials from nanocrystal building blocks represents a powerful new paradigm for materials design. Just as nature's materials orchestrate intricate combinations of atoms from the library of the periodic table, nanocrystal "metamaterials" integrate individual nanocrystals into larger architectures with emergent collective properties. The individual nanocrystal "meta-atoms" that make up these materials are themselves each a nanoscale atomic system with tailorable size, shape, and elemental composition, enabling the creation of hierarchical materials with predesigned structure at multiple length scales. However, an improved fundamental understanding of the interactions among individual nanocrystals is needed in order to translate this structural control into enhanced functionality. The ability to form precise arrangements of nanocrystals and measure their collective properties is therefore essential for the continued development of nanocrystal metamaterials. In this dissertation, we utilize template-assisted self-assembly and spatially-resolved spectroscopy to form and characterize individual nanocrystal oligomers. At the intersection of "top-down" and "bottom-up" nanoscale patterning schemes, template-assisted self-assembly combines the design freedom of lithography with the chemical control of colloidal synthesis to achieve unique nanocrystal configurations. Here, we employ shape-selective templates to assemble new plasmonic structures, including heterodimers of Au nanorods and upconversion phosphors, a series of hexagonally-packed Au nanocrystal oligomers, and triangular formations of Au nanorods. Through experimental analysis and numerical simulation, we elucidate the means through which inter-nanocrystal coupling imparts collective optical properties to the plasmonic assemblies. Our self-assembly and measurement strategy offers a versatile platform for exploring optical interactions in a wide range of material systems and application areas.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

NASA Astrophysics Data System (ADS)

Gómez, Luis A.; Menezes, Leonardo de S.; de Araújo, Cid B.; Gonçalves, Rogeria R.; Ribeiro, Sidney J. L.; Messaddeq, Younes

2010-06-01

Frequency upconversion (UC) luminescence in nanocrystalline zirconia (ZrO2) and hafnia (HfO2) doped with Er3+ and Yb3+ was studied under continuous-wave excitation at 980 nm. Samples of ZrO2:Er3+, ZrO2:Er3+/Yb3+, and HfO2:Er3+/Yb3+ were prepared by the sol-gel technique and characterized using x-ray diffraction and electron microscopy. A study of the infrared-to-green and infrared-to-red UC processes was performed including the analysis of the spectral and the temporal behavior. The mechanisms contributing to the UC luminescence were identified as excited state absorption and energy transfer among rare-earth ions.

Enhancing light harvesting and charge transport in organic solar cells via integrating lanthanide-doped upconversation materials

NASA Astrophysics Data System (ADS)

Wang, Fei; Yang, Xiao-Yu; Niu, Meng-si; Feng, Lin; Lv, Cheng-kun; Zhang, Kang-ning; Bi, Peng-qing; Yang, Junliang; Hao, Xiao-Tao

2018-07-01

Irradiation of lanthanide-doped upconversion nanoparticles with infrared light can lead to the emission of visible light, which is subsequently absorbed by the organic photoactive layer resulting in the performance enhancement of organic solar cells (OSCs). In this work, OSCs based on poly (3-hexylthiophene) (P3HT) and Phenyl C61 butyric acid methyl ester (PC61BM) blending ytterbium(III), erbium(III) co-doped sodium yttrium fluoride (NaYF4: Yb3+, Er3+) nanoparticles were fabricated with inverted structures. The results indicated that the short current density (J sc) and fill factor were apparently enhanced from 8.60 mA cm‑2 to 9.31 mA cm‑2 and from 57.96% to 64.84%, respectively, leading to an increment of power conversion efficiency (PCE). The photocurrent improvement may have attributed to the additional absorption light generated from upconversion with 980 nm excitation. The active layers with upconversion nanoparticles were investigated to prove enhanced light harvesting, charge transport and energy transfer from upconversion nanoparticles to P3HT. A synergistic effect of broadening light harvesting, efficient energy transfer process, increased carrier mobility and enhanced exciton dissociation in the polymer bulk heterojunction may contribute to the performance enhancement.

Cysteine optical sensing with an up-conversion host and two chemosensors derived from rhodamine: Construction, characterization and performance

NASA Astrophysics Data System (ADS)

Lin, Chen; Zhigang, Fang

2017-03-01

This paper focused on two rhodamine chemosensors for cysteine optical sensing. To minimize their photobleaching caused by excitation light, up-conversion NaYF4:Yb3 +/Er3 + nanocrystals were prepared and used as excitation host. Photophysical measurement on this host and the two chemosensors suggested that chemosensor absorption matched well with host emission. An efficient energy transfer between them was discussed and confirmed by their spectral analysis and emission lifetime comparison. Job's plot suggested that our chemosensors followed a simple recognition mechanism towards cysteine with binding stoichiometry of 1:1. Both chemosensors showed emission "off-on" effect triggered by cysteine and good photostability. Linear working curves with maximum sensitivity of 2.61 were obtained. S substituent was positive to improve selectivity.

Upconversion-pumped luminescence efficiency of rare-earth-doped hosts sensitized with trivalent ytterbium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Page, R.H.; Schaffers, K.I.; Waide, P.A.

We discuss the upconversion luminescence efficiencies of phosphors that generate red, green, and blue light. The phosphors studied are single crystals and powders co-doped with Er{sup 3+} and Yb{sup 3+}, and with Tm{sup 3+} and Yb{sup 3+}. The Yb ions are pumped near 980 nm; transfers of two or three quanta to the co-doped rare earth ion generate visible luminescence. The main contribution embodied in this work is the quantitative measurement of this upconversion efficiency, based on the use of a calibrated integrating sphere, determination of the fraction of pump light absorbed, and careful control of the pump laser beammore » profile. The green phosphors are the most efficient, yielding efficiency values as high as 4 %, with the red and blue materials giving 1 - 2 %. Saturation was observed in all cases, suggesting that populations of upconversion steps of the ions are maximized at higher power. Quasi-CW modeling of the intensity- dependent upconversion efficiency was attempted; input data included level lifetimes, transition cross sections, and cross-relaxation rate coefficients. The saturation of the Yb,Er:fluoride media is explained as the pumping of Er{sup 3+} ions into a bottleneck (long-lived state)- the {sup 4}I{sub 13/2} metastable level, making them unavailable for further excitation transfer. 32 refs., 5 figs., 3 tabs.« less

Heterogeneous Semiconductor Shells Sequentially Coated on Upconversion Nanoplates for NIR-Light Enhanced Photocatalysis.

PubMed

Cui, Cao; Tou, Meijie; Li, Mohua; Luo, Zhenguo; Xiao, Lingbo; Bai, Song; Li, Zhengquan

2017-02-20

Combination of upconversion nanocrystals (UCNs) with CeO 2 is a decent choice to construct NIR-activated photocatalysts for utilizing the NIR light in the solar spectrum. Herein we present a facile approach to deposit a CeO 2 layer with controllable thickness on the plate-shaped NaYF 4 :Yb,Tm UCNs. The developed core-shell nanocomposites display obvious photocatalytic activity under the NIR light and exhibit enhanced activity under the full solar spectrum. For enhancing the separation of photogenerated electrons and holes on the CeO 2 surface, we sequentially coat a ZnO shell on the nanocomposites so as to form a heterojunction structure for achieving a better activity. The developed hybrid photocatalysts have been characterized with TEM, SEM, PL, etc., and the working mechanism of such UCN-semiconductor heterojunction photocatalysts has been proposed.

Size and shape effects in β-NaGdF4: Yb3+, Er3+ nanocrystals

NASA Astrophysics Data System (ADS)

Noculak, Agnieszka; Podhorodecki, Artur

2017-04-01

Three sets of β-NaGdF4:Yb3+, Er3+ nanocrystals (NCs) with different shapes (spherical and more complex flower shapes), different sizes (6-17 nm) and Yb3+ concentrations (2%-15%) were synthesized by a co-precipitation method using oleic acid as a stabilizing agent. The uncommon, single-crystalline flower-shaped NCs were obtained by simply adjusting the fluorine-to-lanthanides molar ratio. Additionally, some of the NCs with different sizes have been covered by the un-doped shell. The crystal phase, shapes and sizes of all NCs were examined using transmission electron microscopy and x-ray diffraction methods. Simultaneously, upconversion luminescence and lifetimes, under 980 nm excitation, were measured and the changes in green to red (G/R) emission ratios as well as emission decay times were correlated with the evolution of nanocrystal sizes and surface to volume ratios. Three different mechanisms responsible for the changes in G/R ratios were presented and discussed.

Probing the Crystal Structure and Formation Mechanism of Lanthanide-Doped Upconverting Nanocrystals

DOE PAGES

Hudry, Damien; Abeykoon, A. M. M.; Dooryhee, E.; ...

2016-11-23

Lanthanide (Ln)-doped upconverting nanocrystals (UCNCs), such as NaLnF 4 (with Ln = lanthanide), constitute an important class of nanoscale materials due to their capacity to convert near-infrared photons into near-ultraviolet or visible light. Although under intense investigation for more than a decade, UCNCs have been relatively underexplored especially regarding their crystal structure and mechanisms of formation in organic media. The former is needed to explain the relationship between atomic scale structure and upconversion (UC) properties of UCNCs (i.e., local symmetry for 4f–4f transition probability, Ln 3+ distances for energy migration), while the latter is essential to finely tune the size, morphology, chemical composition, and architecture of well-defined upconverting nanostructures, which constitute the experimental levers to modify the optical properties. In this contribution, we use synchrotron-based diffraction experiments coupled to Rietveld and pair distribution function (PDF) analyses to understand the formation of NaGdF 4:Yb:Er UCNCs in organic media and to investigate their crystal structure. Our results reveal a complex mechanism of the formation of NaGdF 4:Yb:Er UCNCs based on chemical reactions involving molecular clusters and in situ-generated, crystalline sodium fluoride at high temperature. Additionally, a detailed crystallographic investigation of NaGdF 4:Yb:Er UCNCs is presented. Our Rietveld and PDF analyses show that the space group Pmore » $$\\bar{6}$$ is the one that best describes the crystal structure of NaGdF 4:Yb:Er UCNCs contrary to what has been recently proposed. Further, our Rietveld and PDF data reveal the formation of bulk-like crystal structure down to 10 nm with limited distortions. Finally, the results presented in this paper constitute an important step toward the comprehensive understanding of the underlying picture that governs UC properties of lanthanide-doped nanostructures.« less

Polymorph (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho-Lu, Y) and REF{sub 3} nanocrystals: Hydrothermal synthesis, characterization and luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Li-Ping; Zhang, Qiang; Yan, Bing, E-mail: byan@tongji.edu.cn

Graphical abstract: A hydrothermal system is developed to prepare one new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O and known rare earth fluorides involving REF{sub 3} nanocrystals under mild condition. Highlights: ► A new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O has been synthesized. ► The RE{sup 3+} radius decides the shape evolution and phase control for REF{sub 3} NCs. ► The RE{sup 3+} radius has influence on the microstructure and morphology of REF{sub 3} NCs. -- Abstract: In this paper, a solvents-thermal system is developed to prepare one new polymorph of (C{sub 2}N{submore » 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O and rare earth fluorides REF{sub 3} nanocrystals under mild condition. It is found that the ionic radius of RE{sup 3+} is the key factor responsible for the shape evolution and phase control for rare earth fluorides nanocrystals at selected temperatures, which has an influence on the microstructure and morphology of the products to some extent. With the increase of the atomic number, the shape of fluoride changes from hexagonal REF{sub 3} phase (RE = La, Sm) to orthorhombic REF{sub 3} phase (RE = Eu-Dy), and finally to diamond structure (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho, Er, Tm, Yb, Lu, Y). In addition, the characteristic energy level transition {sup 5}D{sub 0}–{sup 7}F{sub 1} of Eu{sup 3+} splits into 585 and 591 nm emission peaks, and the dominant peak is the orange emission at 591 nm.« less

Remineralization and repair of enamel surface by biomimetic Zn-carbonate hydroxyapatite containing toothpaste: a comparative in vivo study

PubMed Central

Lelli, Marco; Putignano, Angelo; Marchetti, Marco; Foltran, Ismaela; Mangani, Francesco; Procaccini, Maurizio; Roveri, Norberto; Orsini, Giovanna

2014-01-01

Consumption of acidic foods and drinks and other factors that cause enamel wear are responsible for the daily enamel loss and degradation. Use of some toothpastes that have been showed to possess different properties of remineralisation and/or repair of the enamel surface may help to protect tooth enamel. The aim of this study was to evaluate whether the use of toothpaste containing Zn-carbonate hydroxyapatite (CHA) nanostructured microcrystals may exert remineralization/repair effects of the enamel surface. Two groups of patients, aged between 18 and 75 years, used a Zn-CHA nanocrystals-based toothpaste (experimental group) and a potassium nitrate/sodium fluoride toothpaste (active control group) for 8 weeks. At the end of this period, extractions were performed in five subjects per study group. Negative controls consisted of two subjects treated with non-specified fluoride toothpaste. Teeth were processed for morphological and chemical-physic superficial characterizations by means of Scanning Electronic Microscopy with Elementary analysis, X-Ray Diffraction analysis and Infrared analysis. In this study, the use of a Zn-CHA nanocrystals toothpaste led to a remineralization/repair of the enamel surface, by deposition of a hydroxyapatite-rich coating. On the other hand, the use of both a nitrate potassium/sodium fluoride and non-specified fluoride toothpastes did not appreciably change the enamel surface. In conclusion, this study demonstrates that the toothpaste containing Zn-CHA nanostructured microcrystals, differently from nitrate potassium/sodium fluoride and non-specified fluoride toothpastes, may promote enamel superficial repair by means of the formation of a protective biomimetic CHA coating. PMID:25249980

Synthesis and application of nanohybrids based on upconverting nanoparticles and polymers.

PubMed

Cheng, Ziyong; Lin, Jun

2015-05-01

Lanthanide-doped upconversion nanoparticles (UCNPs) have been an emerging and exciting research field in recent years due to their unique luminescent properties of converting near-infrared light to shorter wavelength radiation. UCNPs offer excellent prospects in luminescent labeling, displays, bioimaging, bioassays, drug delivery, sensors, and anticounterfeiting applications. Along with the abundant studies and rapid progress in this area, UCNPs are promising to be a new class of luminescent probe owing to their special advantages over the conventional organic dyes and quantum dots. Among them, polymers play an important role to improve properties or endow new function of UCNPs such as for matrix materials, water solubility, linking active targeting molecules, biocompatibility, and stimuli-responsive behavior. This article briefly reviews the compositions, optical mechanisms, architectures of upconversion nanocrystals and highlights the works on various functional UCNPs/polymer nanohybrids as well as many new interesting fruits in applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth and optical properties of Pr,Yb-codoped KY 3F 10 fluoride single crystals for up-conversion visible luminescence

NASA Astrophysics Data System (ADS)

Kim, Kyoung Jin; Jouini, Anis; Yoshikawa, Akira; Simura, Rayko; Boulon, Georges; Fukuda, Tsuguo

2007-02-01

We investigate different ways to realize laser emission from (Pr 3+) 3P J=0,1,2 levels by pump sources other than the common argon and excimer-dye laser. The use of infrared (IR) laser diodes in combination with intra- and inter-ionic energy transfer processes (up-conversion) could be an efficient solution towards laser oscillation. Pr 3+,Yb 3+-codoped KY 3F 10 (Pr, Yb:KYF) single crystals were successfully grown by the micro-pulling-down (μ-PD) method. The crystals were transparent with a slightly greenish color, 2.0-2.5 mm in diameter, 20-30 mm in length and free from visible inclusions and cracks. Effective segregation coefficients of Pr and Yb in KYF were studied by means of absorption and chemical analysis. Strong visible emission via selective IR pumping with λ=975 nm and up-conversion excitation were obtained in Pr, Yb:KYF at room temperature (RT). Luminescence measurements have been carried out and the decay kinetics of the Pr 3+ visible emissions was investigated by room temperature time-resolved spectra.

Core-shell-shell heterostructures of α-NaLuF4:Yb/Er@NaLuF4:Yb@MF2 (M = Ca, Sr, Ba) with remarkably enhanced upconversion luminescence.

PubMed

Su, Yue; Liu, Xiuling; Lei, Pengpeng; Xu, Xia; Dong, Lile; Guo, Xianmin; Yan, Xingxu; Wang, Peng; Song, Shuyan; Feng, Jing; Zhang, Hongjie

2016-07-05

Core-shell-shell heterostructures of α-NaLuF4:Yb/Er@NaLuF4:Yb@MF2 (M = Ca, Sr, Ba) have been successfully fabricated via the thermal decomposition method. Upconversion nanoparticles (UCNPs) were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), upconversion luminescence (UCL) spectroscopy, etc. Under 980 nm excitation, the emission intensities of the UCNPs are remarkably enhanced after coating the MF2 (M = Ca, Sr, and Ba) shell. Among these samples, CaF2 coated UCNPs show the strongest overall emission, while BaF2 coated UCNPs exhibit the longest lifetime. These results demonstrate that alkaline earth metal fluorides are ideal materials to improve the UCL properties. Meanwhile, although the lattice mismatch between the ternary NaREF4 core and the binary MF2 (M = Sr and Ba) shell is relatively large, the successfully synthesized NaLuF4:Yb/Er@NaLuF4:Yb@MF2 indicates a new outlook on the fabrication of heterostructural core-shell UCNPs.

NaF-loaded core-shell PAN-PMMA nanofibers as reinforcements for Bis-GMA/TEGDMA restorative resins.

PubMed

Cheng, Liyuan; Zhou, Xuegang; Zhong, Hong; Deng, Xuliang; Cai, Qing; Yang, Xiaoping

2014-01-01

A kind of core-shell nanofibers containing sodium fluoride (NaF) was produced and used as reinforcing materials for dimethacrylate-based dental restorative resins in this study. The core-shell nanofibers were prepared by coaxial-electrospinning with polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) solutions as core and shell fluids, respectively. The produced PAN-PMMA nanofibers varied in fiber diameter and the thickness of PMMA shell depending on electrospinning parameters. NaF-loaded nanofibers were obtained by incorporating NaF nanocrystals into the core fluid at two loadings (0.8 or 1.0wt.%). Embedment of NaF nanocrystals into the PAN core did not damage the core-shell structure. The addition of PAN-PMMA nanofibers into Bis-GMA/TEGDMA clearly showed the reinforcement due to the good interfacial adhesion between fibers and resin. The flexural strength (Fs) and flexural modulus (Ey) of the composites decreased slightly as the thickness of PMMA shell increasing. Sustained fluoride releases with minor initial burst release were achieved from NaF-loaded core-shell nanofibers and the corresponding composites, which was quite different from the case of embedding NaF nanocrystals into the dental resin directly. The study demonstrated that NaF-loaded PAN-PMMA core-shell nanofibers were not only able to improve the mechanical properties of restorative resin, but also able to provide sustained fluoride release to help in preventing secondary caries. © 2013.

Ultrafast exciton dynamics in cadmium selenide nanocrystals determined by femtosecond fluorescence upconversion spectroscopy

NASA Astrophysics Data System (ADS)

Underwood, David Frederick

Femtosecond fluorescence upconversion spectroscopy is a technique that allows the unambiguous determination of the excited state dynamics of an analyte. Combining this method with the use of tunable laser excitation, the exciton dynamics in semiconducting nanocrystals (NC's) of cadmium selenide (CdSe) have been determined, devoid of the complications arising from more common spectroscopic methods such as pump-probe. The results of this investigation were used to construct a model to fully describe the three-level system comprising of the valence and conduction bands and surface states, which have been calculated by others to lie mid-gap in energy. Smaller NC's showed faster decay components due to increased interaction between the exciton and surface states. The deep trap emission, which has never before been measured by ultrafast fluorescence techniques, shows a rapid rise time (˜2 ps), which is attributed to surface selenium dangling bonds relaxing to the valence band and radiatively combining with the photo-generated hole. The band edge fluorescence decays as the deep trap emission grows in, inherently coupling the two processes. An experiment which measured the dependence of the excitation energy showed that increased energy imparted to the NC's resulted in increased rise times, yielding the timescales for exciton relaxation through the valence and conduction band states to the lowest emitting state. Surface-oxidized and normally-passivated NC's display the same decay dynamics in time but differ in relative amplitude; the latter point agrees with steady-state measurements. The rotational anisotrophy of the NC's was measured and agrees with previous pump-probe data. Upconversion on the red and blue sides of the static fluorescence spectrum showed no discernable differences, which is either and inherent limitation of the experimental apparatus, or the possibility that lower-lying triplet states are populated on a timescale below the instrument resolution.

Er3+ -doped anatase TiO2 nanocrystals: crystal-field levels, excited-state dynamics, upconversion, and defect luminescence.

PubMed

Luo, Wenqin; Fu, Chengyu; Li, Renfu; Liu, Yongsheng; Zhu, Haomiao; Chen, Xueyuan

2011-11-04

A comprehensive survey of electronic structure and optical properties of rare-earth ions embedded in semiconductor nanocrystals (NCs) is of vital importance for their potential applications in areas as diverse as luminescent bioprobes, lighting, and displays. Er3+ -doped anatase TiO2 NCs, synthesized via a facile sol-gel solvothermal method, exhibit intense and well-resolved intra-4f emissions of Er3+ . Crystal-field (CF) spectra of Er3+ in TiO2 NCs are systematically studied by means of high-resolution emission and excitation spectra at 10-300 K. The CF analysis of Er3+ assuming a site symmetry of C(2v) yields a small root-mean-square deviation of 25.1 cm(-1) and reveals the relatively large CF strength (549 cm(-1) ) of Er3+, thus verifying the rationality of the C(2v) symmetry assignment of Er3+ in anatase TiO2 NCs. Based on a simplified thermalization model for the temperature-dependent photoluminescence (PL) dynamics from (4) S(3/2) , the intrinsic radiative luminescence lifetimes of (4) S(3/2) and (2) H(11/2) are experimentally determined to be 3.70 and 1.73 μs, respectively. Green and red upconversion (UC) luminescence of Er3+ can be achieved upon laser excitation at 974.5 nm. The UC intensity of Er3+ in Yb/Er-codoped NCs is found to be about five times higher than that of Er-singly-doped counterparts as a result of efficient Yb3+ sensitization and energy transfer upconversion (ETU) evidenced by its distinct UC luminescence dynamics. Furthermore, the origin of defect luminescence is revealed based on the temperature-dependent PL spectra upon excitation above the TiO2 bandgap at 325 nm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of La0.2Ce0.6Eu0.2F3 nanocrystals capped with polyethylene glycol on human pancreatic cancer cells in vitro

NASA Astrophysics Data System (ADS)

Withers, Nathan J.; Glazener, Natasha N.; Rivera, Antonio C.; Akins, Brian A.; Armijo, Leisha M.; Plumley, John B.; Cook, Nathaniel C.; Sugar, Jacqueline M.; Chan, Rana; Brandt, Yekaterina I.; Smolyakov, Gennady A.; Heintz, Philip H.; Osiński, Marek

2013-02-01

Lanthanide fluoride colloidal nanocrystals offer a way to improve the diagnosis and treatment of cancer through the enhanced absorption of ionizing radiation, in addition to providing visible luminescence. In order to explore this possibility, tests with a kilovoltage therapy unit manufactured by the Universal X-Ray Company were performed to estimate the energy sensitivity of this technique. La0.2Ce0.6Eu0.2F3 nanocrystals capped with polyethylene glycol of molecular weight 6000 were synthesized, suspended in deionized water, and made tolerant to biological ionic pressures by incubation with fetal bovine serum. These nanocrystals were characterized by dynamic light scattering, muffle furnace ashing, and photoluminescence spectroscopy. Clonogenic assays were performed on the cells to assay the cytotoxicity and radiotoxicity of the nanocrystals on the human pancreatic cancer cell line PANC-1, purchased from ATCC.

Remote activation and detection of up-converted luminescence via surface plasmon polaritons propagating in a silver nanowire.

PubMed

Prymaczek, A; Cwierzona, M; Grzelak, J; Kowalska, D; Nyk, M; Mackowski, S; Piatkowski, D

2018-06-27

In this paper, we demonstrate remote activation and detection of the 2-photon up-conversion luminescence via surface plasmon polaritons propagating in a long silver nanowire. The hybrid nanostructure was assembled by locally depositing a submicron droplet of nanocrystal-containing colloidal solution on one of the ends of the metallic nanowire. When - using a classic confocal microscope - the second end of the nanowire, without the nanocrystals, is illuminated with infrared laser light, we observe strong emission from the same end. Therefore, it indicates that surface plasmon polaritons activated with infrared light at the second end of the nanowire propagate along it and can excite nanocrystals in the droplet at the opposite end. Subsequently, the excited nanocrystals up-convert the energy and by launching surface plasmon polaritons can guide the up-converted luminescence back to the starting point. The emergence of this effect is much more pronounced for a laser polarized along the nanowire. The spectral and temporal character of this emission reveals strong interactions between surface plasmon polaritons and electronic states of the nanocrystals. The details of local and non-local aspects of the effects of remote excitation and guiding of energy in a silver nanowire are elucidated using a unique experimental setup, based on two microscope objectives for spatial separation and control of both excitation and emission beams.

Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator.

PubMed

Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

2014-03-01

Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF 3 :Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd 3+ and Tb 3+ ions in the nanocrystals enhances the scintillation efficiency.

Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator

PubMed Central

Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

2014-01-01

Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF3:Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd3+ and Tb3+ ions in the nanocrystals enhances the scintillation efficiency. PMID:24610960

Accurate thermometry based on the red and green fluorescence intensity ratio in NaYF₄: Yb, Er nanocrystals for bioapplication.

PubMed

Liu, Lixin; Qin, Feng; Lv, Tianquan; Zhang, Zhiguo; Cao, Wenwu

2016-10-15

A biological temperature measurement method based on the fluorescence intensity ratio (FIR) was developed to reduce uncertainty. The upconversion luminescence of NaYF₄:Yb, Er nanocrystals was studied as a function of temperature around the physiologically relevant range of 300-330 K. We found that the green-green FIR Fe and red-green FIR (I₆₆₀/I₅₄₀) varied linearly as temperature increased. The thermometric uncertainties using the two FIRs were discussed and were determined to be almost constant at 0.6 and 0.09 K for green-green and red-green, respectively. The lower thermometric uncertainty comes from the intense signal-to-noise ratio of the measured FIRs owing to their comparable fluorescence intensities.

Enhanced Cellular Ablation by Attenuating Hypoxia Status and Reprogramming Tumor-Associated Macrophages via NIR Light-Responsive Upconversion Nanocrystals.

PubMed

Ai, Xiangzhao; Hu, Ming; Wang, Zhimin; Lyu, Linna; Zhang, Wenmin; Li, Juan; Yang, Huanghao; Lin, Jun; Xing, Bengang

2018-04-18

Near-infrared (NIR) light-mediated photodynamic therapy (PDT), especially based on lanthanide-doped upconversion nanocrystals (UCNs), have been extensively investigated as a promising strategy for effective cellular ablation owing to their unique optical properties to convert NIR light excitation into multiple short-wavelength emissions. Despite the deep tissue penetration of NIR light in living systems, the therapeutic efficiency is greatly restricted by insufficient oxygen supply in hypoxic tumor microenvironment. Moreover, the coexistent tumor-associated macrophages (TAMs) play critical roles in tumor recurrence during the post-PDT period. Herein, we developed a unique photosensitizer-loaded UCNs nanoconjugate (PUN) by integrating manganese dioxide (MnO 2 ) nanosheets and hyaluronic acid (HA) biopolymer to improve NIR light-mediated PDT efficacy through attenuating hypoxia status and synergistically reprogramming TAMs populations. After the reaction with overproduced H 2 O 2 in acidic tumor microenvironment, the MnO 2 nanosheets were degraded for the production of massive oxygen to greatly enhance the oxygen-dependent PDT efficiency upon 808 nm NIR light irradiation. More importantly, the bioinspired polymer HA could effectively reprogram the polarization of pro-tumor M2-type TAMs to anti-tumor M1-type macrophages to prevent tumor relapse after PDT treatment. Such promising results provided the great opportunities to achieve enhanced cellular ablation upon NIR light-mediated PDT treatment by attenuating hypoxic tumor microenvironment, and thus facilitated the rational design of new generations of nanoplatforms toward immunotherapy to inhibit tumor recurrence during post-PDT period.

Direct Evidence of Significant Cation Intermixing in Upconverting Core@Shell Nanocrystals: Toward a New Crystallochemical Model

DOE PAGES

Hudry, Damien; Busko, Dmitry; Popescu, Radian; ...

2017-11-02

Core@shell design represents an important class of architectures because of its capability to dramatically increase the absolute upconversion quantum yield (UCQY) of upconverting nanocrystals (UCNCs) but also to tune energy migration pathways. A relatively new trend towards the use of very thick optically inert shells affording significantly higher absolute UCQYs raises the question of the crystallographic and chemical characteristics of such nanocrystals (NCs). In this article, local chemical analyses performed by scanning transmission electron microscopy (STEM) combined with energy dispersive x-ray spectroscopy (EDXS) and x-ray total scattering experiments together with pair distribution function (PDF) analyses were used to probe themore » local chemical and structural characteristics of hexagonal β-NaGd0.78Yb0.2Er0.02F4@NaYF4 core@shell UCNCs. The investigations lead to a new crystallochemical model to describe core@shell UCNCs that considerably digresses from the commonly accepted epitaxial growth concept with sharp interfaces. The results obtained on ultra-small (4.8 ± 0.5 nm) optically active cores (β-NaGd0.78Yb0.2Er0.02F4) surrounded by an optically inert shell (NaYF4) of tunable thickness (roughly 0, 1, 2, and 3.5 nm) clearly indicate the massive dissolution of the starting seeds and the inter-diffusion of the shell element (such as Y) into the Gd/Yb/Er-containing core giving rise to the formation of a non-homogeneous solid solution characterized by concentration gradients and the lack of sharp interfaces. Independently of the inert shell thickness, core/interface/shell architectures were observed for all synthesized UCNCs. The presented results constitute a significant step towards the comprehensive understanding of the “structure - property” relationship of upconverting core@shell architectures, which is of prime interest not only in the development of more efficient structures but also to provide new physical insights at the nanoscale to better explain upconversion (UC) properties alterations.« less

Direct Evidence of Significant Cation Intermixing in Upconverting Core@Shell Nanocrystals: Toward a New Crystallochemical Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hudry, Damien; Busko, Dmitry; Popescu, Radian

Core@shell design represents an important class of architectures because of its capability to dramatically increase the absolute upconversion quantum yield (UCQY) of upconverting nanocrystals (UCNCs) but also to tune energy migration pathways. A relatively new trend towards the use of very thick optically inert shells affording significantly higher absolute UCQYs raises the question of the crystallographic and chemical characteristics of such nanocrystals (NCs). In this article, local chemical analyses performed by scanning transmission electron microscopy (STEM) combined with energy dispersive x-ray spectroscopy (EDXS) and x-ray total scattering experiments together with pair distribution function (PDF) analyses were used to probe themore » local chemical and structural characteristics of hexagonal β-NaGd0.78Yb0.2Er0.02F4@NaYF4 core@shell UCNCs. The investigations lead to a new crystallochemical model to describe core@shell UCNCs that considerably digresses from the commonly accepted epitaxial growth concept with sharp interfaces. The results obtained on ultra-small (4.8 ± 0.5 nm) optically active cores (β-NaGd0.78Yb0.2Er0.02F4) surrounded by an optically inert shell (NaYF4) of tunable thickness (roughly 0, 1, 2, and 3.5 nm) clearly indicate the massive dissolution of the starting seeds and the inter-diffusion of the shell element (such as Y) into the Gd/Yb/Er-containing core giving rise to the formation of a non-homogeneous solid solution characterized by concentration gradients and the lack of sharp interfaces. Independently of the inert shell thickness, core/interface/shell architectures were observed for all synthesized UCNCs. The presented results constitute a significant step towards the comprehensive understanding of the “structure - property” relationship of upconverting core@shell architectures, which is of prime interest not only in the development of more efficient structures but also to provide new physical insights at the nanoscale to better explain upconversion (UC) properties alterations.« less

Enhancement of a-Si:H solar cell efficiency by Y2O3 : Yb3+, Er3+ near infrared spectral upconverter

NASA Astrophysics Data System (ADS)

Markose, Kurias K.; Anjana, R.; Subha, P. P.; Antony, Aldrin; Jayaraj, M. K.

2016-09-01

The optical properties of Yb3+/Er3+ doped Y2O3 upconversion phosphor and the enhancement of efficiency of a-Si:H solar cell on incorporation of upconverter are investigated. The Y2O3 host material has high corrosion resistance, thermal stability, chemical stability, low toxicity and relatively low phonon energy (≈ 500 cm-1). Y2O3:Yb3+ (x %): Er3+ (y %) upconversion nanophosphors with different dopant concentrations were synthesized via simple hydrothermal method followed by a heat treatment at 1200°C for 12 hrs. Highly crystalline, quasi-spherical, body centered cubic Y2O3 structure was obtained. The structure, phase and morphology of the nanocrystals were determined using x-ray diffraction and SEM. Following pumping at 980 nm two dominant emission bands were observed at about 550 nm(green) and 660 nm(red), corresponding to 2H11/2, 4S3/2 -> 4I15/2 and 4F9/2 -> 4I15/2 transitions respectively. The dependence of emission intensity on pump power shows that the mechanism involved is two photon absorption. The upconversion phosphor along with a binder is coupled behind the a-Si:H solar cell which absorbs transmitted sub-band-gap photons and emits back the upconverted visible light which can be absorbed by the solar cell. Under suitable intensity of illumination the solar cell short circuit current is found to be increased on adding the upconversion layer.

Decorating fiber nanotip with single perovskite quantum dot and other luminescent nanocrystals synthesized in oil-phase

NASA Astrophysics Data System (ADS)

Qian, Yu; Xing, Xing; Xu, Ya; Lu, Zhenda; Zhang, Weihua

2017-11-01

We report a simple yet robust method for fabricating single perovskite quantum dot (QD) decorated fiber nanotips. In this method, a single QD is directly picked up and subsequently glued on the apex of a specially fabricated cantilever fiber tip with a high success rate (approx. 70%) without using expensive close-loop feedback systems. Thanks to the flexibility and robustness of the fiber tips, no damage of the tips was observed in the process. Moreover, nanocrystal (NC) dispersing technique was developed to avoid undesired aggregations of QDs, and it guarantees that only one QD is glued each time. Finally, we demonstrate that this technique can also be applied to other oil-phase synthesized NCs, including CdSe QDs and upconversion luminescent NCs. It leads to many important applications on probing the local environment using high performance luminescent nanoprobes.

Tuning the autophagy-inducing activity of lanthanide-based nanocrystals through specific surface-coating peptides

NASA Astrophysics Data System (ADS)

Zhang, Yunjiao; Zheng, Fang; Yang, Tianlong; Zhou, Wei; Liu, Yun; Man, Na; Zhang, Li; Jin, Nan; Dou, Qingqing; Zhang, Yong; Li, Zhengquan; Wen, Long-Ping

2012-09-01

The induction of autophagy on exposure of cells to a variety of nanoparticles represents both a safety concern and an application niche for engineered nanomaterials. Here, we show that a short synthetic peptide, RE-1, identified by means of phage display, binds to lanthanide (LN) oxide and upconversion nanocrystals (UCN), forms a stable coating layer on the nanoparticles’ surface, and effectively abrogates their autophagy-inducing activity. Furthermore, RE-1 peptide variants exhibit a differentially reduced binding capability, and correspondingly, a varied ability to reduce the autophagic response. We also show that the addition of an arginine-glycine-aspartic acid (RGD) motif to RE-1 enhances autophagy for LN UCN through the interaction with integrins. RE-1 and its variants provide a versatile tool for tuning material-cell interactions to achieve the desired level of autophagy, and may prove useful for the various diagnostic and therapeutic applications of LN-based nanomaterials and nanodevices.

In vivo covalent cross-linking of photon-converted rare-earth nanostructures for tumour localization and theranostics

NASA Astrophysics Data System (ADS)

Ai, Xiangzhao; Ho, Chris Jun Hui; Aw, Junxin; Attia, Amalina Binte Ebrahim; Mu, Jing; Wang, Yu; Wang, Xiaoyong; Wang, Yong; Liu, Xiaogang; Chen, Huabing; Gao, Mingyuan; Chen, Xiaoyuan; Yeow, Edwin K. L.; Liu, Gang; Olivo, Malini; Xing, Bengang

2016-01-01

The development of precision nanomedicines to direct nanostructure-based reagents into tumour-targeted areas remains a critical challenge in clinics. Chemical reaction-mediated localization in response to tumour environmental perturbations offers promising opportunities for rational design of effective nano-theranostics. Here, we present a unique microenvironment-sensitive strategy for localization of peptide-premodified upconversion nanocrystals (UCNs) within tumour areas. Upon tumour-specific cathepsin protease reactions, the cleavage of peptides induces covalent cross-linking between the exposed cysteine and 2-cyanobenzothiazole on neighbouring particles, thus triggering the accumulation of UCNs into tumour site. Such enzyme-triggered cross-linking of UCNs leads to enhanced upconversion emission upon 808 nm laser irradiation, and in turn amplifies the singlet oxygen generation from the photosensitizers attached on UCNs. Importantly, this design enables remarkable tumour inhibition through either intratumoral UCNs injection or intravenous injection of nanoparticles modified with the targeting ligand. Our strategy may provide a multimodality solution for effective molecular sensing and site-specific tumour treatment.

M2+ Doping Induced Simultaneous Phase/Size Control and Remarkable Enhanced Upconversion Luminescence of NaLnF4 Probes for Optical-Guided Tiny Tumor Diagnosis.

PubMed

Li, Youbin; Li, Xiaolong; Xue, Zhenluan; Jiang, Mingyang; Zeng, Songjun; Hao, Jianhua

2017-05-01

Doping has played a vital role in constructing desirable hybrid materials with tunable functions and properties via incorporating atoms into host matrix. Herein, a simple strategy for simultaneously modifying the phase, size, and upconversion luminescence (UCL) properties of the NaLnF 4 (Ln = Y, Yb) nanocrystals by high-temperature coprecipitation through nonequivalent M 2+ doping (M = Mg 2+ , Co 2+ ) has been demonstrated. The phase transformation from cubic to hexagonal is readily achieved by doping M 2+ . Compared with Mg-free sample, a remarkable enhancement of overall UCL (≈27.5 times) is obtained by doping Mg 2+ . Interestingly, owing to the efficient UCL, red UCL-guided tiny tumor (down to 3 mm) diagnosis is demonstrated for the first time. The results open up a new way of designing high efficient UCL probe with combination of hexagonal phase and small size for tiny tumor detection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Luminescence properties of Tm3+ ions single-doped YF3 materials in an unconventional excitation region.

PubMed

Chen, Yuan; Liu, Qing; Lin, Han; Yan, Xiaohong

2018-05-01

According to the spectral distribution of solar radiation at the earth's surface, under the excitation region of 1150 to 1350 nm, the up-conversion luminescence of Tm 3+ ions was investigated. The emission bands were matched well with the spectral response region of silicon solar cells, achieved by Tm 3+ ions single-doped yttrium fluoride (YF 3 ) phosphor, which was different from the conventional Tm 3+ /Yb 3+ ion couple co-doped materials. Additionally, the similar emission bands of Tm 3+ ions were achieved under excitation in the ultraviolet region. It is expected that via up-conversion and down-conversion routes, Tm 3+ -sensitized materials could convert photons to the desired wavelengths in order to reduce the energy loss of silicon solar cells, thereby enhancing the photovoltaic efficiency. Copyright © 2018 John Wiley & Sons, Ltd.

Polarization-dependent extraordinary optical transmission from upconversion nanoparticles.

PubMed

Wang, Peng Hui; Salcedo, Walter J; Pichaandi, Jothirmayanantham; van Veggel, Frank C J M; Brolo, Alexandre G

2015-11-21

Enhanced upconversion (UC) emission was experimentally demonstrated using gold double antenna nanoparticles coupled to nanoslits in gold films. The transmitted red emission from UC ytterbium and erbium co-doped sodium yttrium fluoride (NaYF4:Yb(3+)/Er(3+)) nanoparticles (UC NPs) at ∼665 nm (excited with a 980 nm diode laser) was enhanced relative to the green emission at ∼550 nm. The relatively enhanced UC NP emission could be tuned by the different polarization-dependent extraordinary optical transmission modes coupled to the gold nanostructures. Finite-difference time-domain calculations suggest that the preferential enhanced UC emission is related to a combination of different surface plasmon mode excitation coupling to cavity Fabry-Perot interactions. A maximum UC enhancement of 6-fold was measured for nanoslit arrays in the absence of the double antennas. In the presence of the double nanoantennas inside the nanoslits, the UC enhancement was between 2- and 4-fold, depending on the experimental conditions.

Lanthanide-doped upconversion nanocrystals: Synthesis and optical properties study

NASA Astrophysics Data System (ADS)

Sun, Qiang

Upconversion phosphor materials have attracted considerable attention in recent years for their potential applications in a wide range of fields, including three-dimensional displays technologies, bio-imaging and photovoltaics. This dissertation aims to develop novel lanthanide-doped upconversion luminescent nanomaterials by using wet chemistry methods. Considerable efforts have been devoted to manipulating the optical properties of the synthesized lanthanide-doped nanoparticles under excitation of different wavelengths, for example, 808, 980 and 1532 nm. In the first research work, a novel core-shell-shell design has been developed for finely tuning of energy migration upconversion of activators without long-lived mediated states, such as Eu3+ and Tb3+ upon excitation at 808 nm by using Nd3+ as sensitizer. Exquisite control the composition of each layer gives rise to maximized upconversion emissions of the activators. For example, with the use of core layer for energy harvesting (NaGdF4:Yb/Nd, active core), the optimal doping concentrations of Eu3+ and Tb3+ is fixed to 15 and 15 mol%, respectively. In contrast, active shell can also provide access to strong upconversion of Eu3+ and Tb3+ by doping Nd (40 mol%) into the outmost layer. Note that the effect of active shell is much stronger than active core in generating upconversion emissions of Eu3+ and Tb3+. Next, upconversion emission tuning of Er/Tm/Yb-doped NaYF4 upconversion nanoparticles has been conducted under excitation at 1532 nm. The output color of the nanoparticles is tunable by changing the doping levels of the lanthanides. With the use of core-shell design, the optical properties of the doped nanoparticles can be further optimized, for example, strongest upconversion emission was observed for NaYF4:Er(10 mol%) NaYF4:Er(0.5 mol%) with a relative emission of green-to-red of 1.2. This work provides a new dimension to control the color output of upconversion nanoparticles. It should be noted that the emission profiles of upconversion nanoparticles will be further enriched by using a combination of different excitation wavelengths. Finally, the orthorhombic-phase K2YF5 nanobelts doped with upconverting lanthanide ions (Er3+ and Tm3+) were synthesized by using a coprecipitation method. The growth kinetics of the nanobelts can be regulated by either control of the volume ratio of oleic acid in the synthetic system or period of reaction time. It was found that desirable lanthanide-doped K2YF5 nanobelts were yielded through the use of long time high-temperature annealing treatment (270 °C, 6 h) in the presence of low content of oleic acid. The assynthesized lanthanide-doped K2YF5 nanobelts show intense upconversion emissions upon excitation at 980 nm. For example, bright yellow emission was observed from K2YF5:Yb/Er(18/2 mol%), resulting from weak optical transitions of 2H11/2 → 4I15/2 (520 nm) and 4S3/2 → 4I15/2 (540 nm) and a dominant transition of 4F9/2 → 4I15/2 (centered at 650 nm) of the doped Er3+. In the case of K2YF5:Yb/Tm(30/0.5 mol%) nanobelts, three main emission bands centered at 479 (blue), 650 (red) and 800 nm (NIR) corresponding to 1D2 → 3H6, 1D2 → 3H4, and 3H4 ¨ 3H6 transition of Tm3+ were observed.

Boosting the down-shifting luminescence of rare-earth nanocrystals for biological imaging beyond 1500 nm.

PubMed

Zhong, Yeteng; Ma, Zhuoran; Zhu, Shoujun; Yue, Jingying; Zhang, Mingxi; Antaris, Alexander L; Yuan, Jie; Cui, Ran; Wan, Hao; Zhou, Ying; Wang, Weizhi; Huang, Ngan F; Luo, Jian; Hu, Zhiyuan; Dai, Hongjie

2017-09-29

In vivo fluorescence imaging in the near-infrared region between 1500-1700 nm (NIR-IIb window) affords high spatial resolution, deep-tissue penetration, and diminished auto-fluorescence due to the suppressed scattering of long-wavelength photons and large fluorophore Stokes shifts. However, very few NIR-IIb fluorescent probes exist currently. Here, we report the synthesis of a down-conversion luminescent rare-earth nanocrystal with cerium doping (Er/Ce co-doped NaYbF 4 nanocrystal core with an inert NaYF 4 shell). Ce doping is found to suppress the up-conversion pathway while boosting down-conversion by ~9-fold to produce bright 1550 nm luminescence under 980 nm excitation. Optimization of the inert shell coating surrounding the core and hydrophilic surface functionalization minimize the luminescence quenching effect by water. The resulting biocompatible, bright 1550 nm emitting nanoparticles enable fast in vivo imaging of blood vasculature in the mouse brain and hindlimb in the NIR-IIb window with short exposure time of 20 ms for rare-earth based probes.Fluorescence imaging in the near-infrared window between 1500-1700 nm (NIR-IIb window) offers superior spatial resolution and tissue penetration depth, but few NIR-IIb probes exist. Here, the authors synthesize rare earth down-converting nanocrystals as promising fluorescent probes for in vivo imaging in this spectral region.

Taking the temperature of the interiors of magnetically heated nanoparticles.

PubMed

Dong, Juyao; Zink, Jeffrey I

2014-05-27

The temperature increase inside mesoporous silica nanoparticles induced by encapsulated smaller superparamagnetic nanocrystals in an oscillating magnetic field is measured using a crystalline optical nanothermometer. The detection mechanism is based on the temperature-dependent intensity ratio of two luminescence bands in the upconversion emission spectrum of NaYF4:Yb(3+), Er(3+). A facile stepwise phase transfer method is developed to construct a dual-core mesoporous silica nanoparticle that contains both a nanoheater and a nanothermometer in its interior. The magnetically induced heating inside the nanoparticles varies with different experimental conditions, including the magnetic field induction power, the exposure time to the magnetic field, and the magnetic nanocrystal size. The temperature increase of the immediate nanoenvironment around the magnetic nanocrystals is monitored continuously during the magnetic oscillating field exposure. The interior of the nanoparticles becomes much hotter than the macroscopic solution and cools to the temperature of the ambient fluid on a time scale of seconds after the magnetic field is turned off. This continuous absolute temperature detection method offers quantitative insight into the nanoenvironment around magnetic materials and opens a path for optimizing local temperature controls for physical and biomedical applications.

Study of TiO2 anatase nano and microstructures with dominant {001} facets for NO oxidation.

PubMed

Sofianou, Maria-Veronica; Trapalis, Christos; Psycharis, Vassils; Boukos, Nikos; Vaimakis, Tiverios; Yu, Jiaguo; Wang, Wenguang

2012-11-01

TiO(2) anatase nanoplates and hollow microspheres were fabricated by a solvothermal-hydrothermal method using titanium isopropoxide as a titanium precursor and hydrofluoric acid as a capping agent in order to enhance the formation of the {001} crystal facets of the anatase nanocrystals. These different morphological structures of TiO(2) anatase can be achieved by only changing the solvent, keeping the amount of the precursor and of the capping agent identical during the solvothermal-hydrothermal process. After calcination of the samples, the adsorbed fluoride atoms on the {001} crystal facets of the TiO(2) anatase nanocrystals were completely removed from their surface according to XPS analysis. The calcined TiO(2) anatase structures were higher crystallized and the specific surface area of the catalysts increased, enhancing their photocatalytic activity in comparison to the non-calcined TiO(2) anatase structures. All TiO(2) anatase samples with adsorbed as well as non-adsorbed fluoride atoms on their {001} crystal facets, exhibited a higher photonic efficiency than Degussa P25, which was used as a reference. The fluoride free TiO(2) anatase nanoplates exhibited the best photocatalytic activity in oxidizing the NO gas to NO(2) and NO(3) (-).

Multifunctional Optical Sensors for Nanomanometry and Nanothermometry: High-Pressure and High-Temperature Upconversion Luminescence of Lanthanide-Doped Phosphates-LaPO4/YPO4:Yb3+-Tm3.

PubMed

Runowski, Marcin; Shyichuk, Andrii; Tymiński, Artur; Grzyb, Tomasz; Lavín, Víctor; Lis, Stefan

2018-05-23

Upconversion luminescence of nano-sized Yb 3+ and Tm 3+ codoped rare earth phosphates, that is, LaPO 4 and YPO 4 , has been investigated under high-pressure (HP, up to ∼25 GPa) and high-temperature (293-773 K) conditions. The pressure-dependent luminescence properties of the nanocrystals, that is, energy red shift of the band centroids, changes of the band ratios, shortening of upconversion lifetimes, and so forth, make the studied nanomaterials suitable for optical pressure sensing in nanomanometry. Furthermore, thanks to the large energy difference (∼1800 cm -1 ), the thermalized states of Tm 3+ ions are spectrally well-separated, providing high-temperature resolution, required in optical nanothermometry. The temperature of the system containing such active nanomaterials can be determined on the basis of the thermally induced changes of the Tm 3+ band ratio ( 3 F 2,3 → 3 H 6 / 3 H 4 → 3 H 6 ), observed in the emission spectra. The advantage of such upconverting optical sensors is the use of near-infrared light, which is highly penetrable for many materials. The investigated nanomanometers/nanothermometers have been successfully applied, as a proof-of-concept of a novel bimodal optical gauge, for the determination of the temperature of the heated system (473 K), which was simultaneously compressed under HP (1.5 and 5 GPa).

Preparation and Characterization of High-Purity Metal Fluorides for Photonic Applications

DTIC Science & Technology

2011-01-01

I . Epstein and M. Sheik- Bahae , “Optical Refrigeration in Solids: Fun- damentals and Overview”; pp. 1–32 in Optical Refrigeration. Science and...Applications of Laser Cooling of Solids, Edited by R. I . Epstein and M. Sheik- Bahae . Wiley, Weinheim, 2009. 12W. G. Rellergert, D. DeMille, R. R. Greco, M. P...Green and Blue Emitting Upconversion Phosphors,” Chem. Mater., 16, 1244–51 (2004). 39W. M. Patterson, D. V. Seletskiy, M. Sheik- Bahae , R. I . Epstein

An upconverted photonic nonvolatile memory.

PubMed

Zhou, Ye; Han, Su-Ting; Chen, Xian; Wang, Feng; Tang, Yong-Bing; Roy, V A L

2014-08-21

Conventional flash memory devices are voltage driven and found to be unsafe for confidential data storage. To ensure the security of the stored data, there is a strong demand for developing novel nonvolatile memory technology for data encryption. Here we show a photonic flash memory device, based on upconversion nanocrystals, which is light driven with a particular narrow width of wavelength in addition to voltage bias. With the help of near-infrared light, we successfully manipulate the multilevel data storage of the flash memory device. These upconverted photonic flash memory devices exhibit high ON/OFF ratio, long retention time and excellent rewritable characteristics.

Fast and long-range triplet exciton diffusion in metal-organic frameworks for photon upconversion at ultralow excitation power.

PubMed

Mahato, Prasenjit; Monguzzi, Angelo; Yanai, Nobuhiro; Yamada, Teppei; Kimizuka, Nobuo

2015-09-01

The conversion of low-energy light into photons of higher energy based on sensitized triplet-triplet annihilation upconversion (TTA-UC) has emerged as a promising wavelength-shifting methodology because it permits UC at excitation powers as low as the solar irradiance. However, its application has been significantly hampered by the slow diffusion of excited molecules in solid matrices. Here, we introduce metal-organic frameworks (MOFs) that promote TTA-UC by taking advantage of triplet exciton migration among fluorophores that are regularly aligned with spatially controlled chromophore orientations. We synthesized anthracene-containing MOFs with different molecular orientations, and the analysis of TTA-UC emission kinetics unveiled a high triplet diffusion rate with a micrometre-scale diffusion length. Surface modification of MOF nanocrystals with donor molecules and their encapsulation in glassy poly(methyl methacrylate) (PMMA) allowed the construction of molecular-diffusion-free solid-state upconverters, which lead to an unprecedented maximization of overall UC quantum yield at excitation powers comparable to or well below the solar irradiance.

Chemical sensing and imaging based on photon upconverting nano- and microcrystals: a review

NASA Astrophysics Data System (ADS)

Christ, Simon; Schäferling, Michael

2015-09-01

The demand for photostable luminescent reporters that absorb and emit light in the red to near-infrared (NIR) spectral region continues in biomedical research and bioanalysis. In recent years, classical organic fluorophores have increasingly been displaced by luminescent nanoparticles. These consist of either polymer or silica based beads that are loaded with luminescent dyes, conjugated polymers, or inorganic nanomaterials such as semiconductor nanocrystals (quantum dots), colloidal clusters of silver and gold, or carbon dots. Among the inorganic materials, photon upconversion nanocrystals exhibit a high potential for application to bioimaging or biomolecular assays. They offer an exceptionally high photostability, can be excited in the NIR, and their anti-Stokes emission enables luminescence detection free of background and perturbing scatter effects even in complex biological samples. These lanthanide doped inorganic crystals have multiple emission lines that can be tuned by the selection of the dopants. This review article is focused on the applications of functionalized photon upconversion nanoparticles (UCNPs) to chemical sensing. This is a comparatively new field of research activity and mainly directed at the sensing and imaging of ubiquitous chemical analytes in biological samples, particularly in living cells. For this purpose, the particles have to be functionalized with suitable indicator dyes or recognition elements, as they do not show an intrinsic or specific luminescence response to most of these analytes (e.g. pH, oxygen, metal ions). We describe the strategies for the design of such responsive nanocomposites utilizing either luminescence resonance energy transfer or emission-reabsorption (inner filter effect) mechanisms and also highlight examples for their use either immobilized in sensor layers or directly as nanoprobes for intracellular sensing and imaging.

BaY2F8 doped with Er3+: An upconverter material for photovoltaic application

NASA Astrophysics Data System (ADS)

Boccolini, A.; Faoro, R.; Favilla, E.; Veronesi, S.; Tonelli, M.

2013-08-01

Fluoride crystals (BaY2F8) doped with Er3+ ions with different doping level have been grown with a home-made Czochralski furnace. A spectroscopic characterization consisting in both absorption and fluorescence measurements were performed in order to investigate the upconversion mechanism occurring when the material is excited with a radiation at 1557 nm. The measured emission spectrum shows a photoluminescence mainly distributed in the Near Infrared (NIR) region at ≃1 μm. The spectral conversion due to the upconversion makes this material suitable for photovoltaic applications, especially if we combine it with a crystalline silicon solar cell. A device made of single face solar cell+upconverter material (PV-UC) was designed and his external quantum efficiency (EQE) at 1557 nm was measured. EQE values of 6.5% and 4.1% were reached under 8.5 W cm-2 power density illumination for the 30%Er3+ and 20%Er3+ samples, respectively.

High Resolution Fluorescence Imaging of Cancers Using Lanthanide Ion-Doped Upconverting Nanocrystals

PubMed Central

Naccache, Rafik; Rodríguez, Emma Martín; Bogdan, Nicoleta; Sanz-Rodríguez, Francisco; de la Cruz, Maria del Carmen Iglesias; de la Fuente, Ángeles Juarranz; Vetrone, Fiorenzo; Jaque, Daniel; Solé, José García; Capobianco, John A.

2012-01-01

During the last decade inorganic luminescent nanoparticles that emit visible light under near infrared (NIR) excitation (in the biological window) have played a relevant role for high resolution imaging of cancer. Indeed, semiconductor quantum dots (QDs) and metal nanoparticles, mostly gold nanorods (GNRs), are already commercially available for this purpose. In this work we review the role which is being played by a relatively new class of nanoparticles, based on lanthanide ion doped nanocrystals, to target and image cancer cells using upconversion fluorescence microscopy. These nanoparticles are insulating nanocrystals that are usually doped with small percentages of two different rare earth (lanthanide) ions: The excited donor ions (usually Yb3+ ion) that absorb the NIR excitation and the acceptor ions (usually Er3+, Ho3+ or Tm3+), that are responsible for the emitted visible (or also near infrared) radiation. The higher conversion efficiency of these nanoparticles in respect to those based on QDs and GNRs, as well as the almost independent excitation/emission properties from the particle size, make them particularly promising for fluorescence imaging. The different approaches of these novel nanoparticles devoted to “in vitro” and “in vivo” cancer imaging, selective targeting and treatment are examined in this review. PMID:24213500

Hydroxyapatite/MCM-41 and SBA-15 Nano-Composites: Preparation, Characterization and Applications

PubMed Central

Anunziata, Oscar A.; Martínez, Maria L.; Beltramone, Andrea R.

2009-01-01

Composites of hydroxyapatite (HaP) and highly ordered large pore mesoporous silica molecular sieves such as, Al-SBA-15 and Al-MCM-41 (denoted as SBA-15 and MCM-41, respectively) were developed, characterized by XRD, BET, FTIR, HRTEM and NMR-MAS, and applied to fluoride retention from contaminated water. The proposed procedure by a new route to prepare the HaP/SBA-15 and HaP/MCM-41, composites generates materials with aluminum only in tetrahedral coordination, according to the 27Al NMR-MAS results. Free OH- groups of HaP nanocrystals, within the hosts, allowed high capacity fluoride retention. The activity of fluoride retention using HaP/MCM-41 or HaP/SBA-15 was 1-2 orders of magnitude greater, respectively, than with pure HaP.

Trigonal LaF3: a novel SRS-active crystal

NASA Astrophysics Data System (ADS)

Kaminskii, A. A.; Lux, O.; Hanuza, J.; Rhee, H.; Eichler, H. J.; Zhang, J.; Tang, D.; Shen, D.; Yoneda, H.; Shirakawa, A.

2014-12-01

Trigonal fluoride LaF3, widely known as a host crystal for Ln3+-lasants, was found to be an attractive many-phonon Raman material and a subject for the investigation of different χ(3)-nonlinear optical effects. We present the manifestation of photon-phonon interactions related to stimulated Raman scattering (SRS) and Raman-induced four-wave mixing (RFWM) processes, initiated by picosecond exсitation at room temperature. Sesqui-octave-spanning Stokes and anti-Stokes frequency comb generation as well as many-step cascaded and cross-cascaded up-conversion χ(3)-nonlinear processes have been observed. The recorded spectral lines originated by SRS and RFWM are identified and attributed to the three observed SRS-promoting phonon modes. The lower limit of the steady-state Raman gain coefficient for near-IR first Stokes generation was estimated. Moreover, a brief review of known Ln3+ : LaF3 laser crystals and SRS-active fluorides is given.

Luminescence in Conjugated Molecular Materials under Sub-bandgap Excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

So, Franky

2014-05-08

Light emission in semiconductors occurs when they are under optical and electrical excitation with energy larger than the bandgap energy. In some low-dimensional semiconductor heterostructure systems, this thermodynamic limit can be violated due to radiative Auger recombination (AR), a process in which the sub-bandgap energy released from a recombined electron-hole pair is transferred to a third particle leading to radiative band-to-band recombination.1 Thus far, photoluminescence up-conversion phenomenon has been observed in some low dimensional semiconductor systems, and the effect is very weak and it can only be observed at low temperatures. Recently, we discovered that efficient electroluminescence in poly[2-methoxy-5-(2’-ethylhexyloxy)-1, phenylenevinylene]more » (MEH-PPV) polymer light-emitting devices (PLEDs) at drive voltages below its bandgap voltage could be observed when a ZnO nanoparticles (NPs) electron injection layer was inserted between the polymer and the aluminum electrode. Specifically, emitted photons with energy of 2.13 eV can be detected at operating voltages as low as 1.2 V at room temperature. Based on these data, we propose that the sub-bandgap turn-on in the MEH-PPV device is due to an Auger-assisted energy up-conversion process. The significance of this discovery is three-fold. First, radiative recombination occurs at operating voltages below the thermodynamic bandgap voltage. This process can significantly reduce the device operating voltage. For example, the current density of the device with the ZnO NC layer is almost two orders of magnitude higher than that of the device without the NC layer. Second, a reactive metal is no longer needed for the cathode. Third, this electroluminescence up-conversion process can be applied to inorganic semiconductors systems as well and their operation voltages of inorganic LEDs can be reduced to about half of the bandgap energy. Based on our initial data, we propose that the sub-bandgap turn-on in MEH-PPV devices is due to Auger-assisted energy up-conversion process. Specifically, we propose that the up-conversion process is due to charge accumulation at the polymer/NPs interface. This model requires that holes should be the dominant carriers in the polymer and the polymer/ZnO NCs heterojunction should be a type II alignment. In order to determine the mechanism of the up-conversion process, we will characterize devices fabricated using polymers with different carrier transporting properties to determine whether hole accumulation at the polymer/nanocrystals is required. Likewise, we will also use NPs with different electronic structures to fabricate devices to determine how electron accumulation affects the up-conversion process. Finally, we will measure quantitatively the interface charge accumulation by electroabsorption and correlate the results with the up-conversion photoluminescence efficiency measurements under an applied electric field.« less

Effect of Pre-Irradiation Annealing and Laser Modification on the Formation of Radiation-Induced Surface Color Centers in Lithium Fluoride

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Novikov, A. N.; Radkevich, A. V.; Runets, L. P.; Stupak, A. P.; Tarasenko, N. V.

2017-01-01

It is shown that surface color centers of the same type are formed in the surface layer and in regions with damaged crystal structure inside crystalline lithium fluoride after γ-irradiation. Results are presented from a study of the effect of pre-irradiation annealing on the efficiency with which surface centers are formed in lithium fluoride nanocrystals. Raising the temperature for pre-irradiation annealing from room temperature to 250°C leads to a substantial reduction in the efficiency with which these centers are created. Surface color centers are not detected after γ-irradiation for pre-irradiation annealing temperatures of 300°C and above. Adsorption of atmospheric gases on the crystal surface cannot be regarded as a necessary condition for the formation of radiation-induced surface centers.

Amplified stimulated emission in upconversion nanoparticles for super-resolution nanoscopy

NASA Astrophysics Data System (ADS)

Liu, Yujia; Lu, Yiqing; Yang, Xusan; Zheng, Xianlin; Wen, Shihui; Wang, Fan; Vidal, Xavier; Zhao, Jiangbo; Liu, Deming; Zhou, Zhiguang; Ma, Chenshuo; Zhou, Jiajia; Piper, James A.; Xi, Peng; Jin, Dayong

2017-02-01

Lanthanide-doped glasses and crystals are attractive for laser applications because the metastable energy levels of the trivalent lanthanide ions facilitate the establishment of population inversion and amplified stimulated emission at relatively low pump power. At the nanometre scale, lanthanide-doped upconversion nanoparticles (UCNPs) can now be made with precisely controlled phase, dimension and doping level. When excited in the near-infrared, these UCNPs emit stable, bright visible luminescence at a variety of selectable wavelengths, with single-nanoparticle sensitivity, which makes them suitable for advanced luminescence microscopy applications. Here we show that UCNPs doped with high concentrations of thulium ions (Tm3+), excited at a wavelength of 980 nanometres, can readily establish a population inversion on their intermediate metastable 3H4 level: the reduced inter-emitter distance at high Tm3+ doping concentration leads to intense cross-relaxation, inducing a photon-avalanche-like effect that rapidly populates the metastable 3H4 level, resulting in population inversion relative to the 3H6 ground level within a single nanoparticle. As a result, illumination by a laser at 808 nanometres, matching the upconversion band of the 3H4 → 3H6 transition, can trigger amplified stimulated emission to discharge the 3H4 intermediate level, so that the upconversion pathway to generate blue luminescence can be optically inhibited. We harness these properties to realize low-power super-resolution stimulated emission depletion (STED) microscopy and achieve nanometre-scale optical resolution (nanoscopy), imaging single UCNPs; the resolution is 28 nanometres, that is, 1/36th of the wavelength. These engineered nanocrystals offer saturation intensity two orders of magnitude lower than those of fluorescent probes currently employed in stimulated emission depletion microscopy, suggesting a new way of alleviating the square-root law that typically limits the resolution that can be practically achieved by such techniques.

Fabrication and Luminescence Characterization of a Silica Nanomatrix Embedded with NaYF4:Yb:Er:Tm@NaGdF4/Fe3O4 Nanoparticles

NASA Astrophysics Data System (ADS)

Thangaraju, Dheivasigamani; Santhana, Vedi; Matsuda, Satoshi; Hayakawa, Yasuhiro

2018-05-01

Hexagonal NaYF4:Yb:Er:Tm@NaGdF4 core-shell nanocrystals were synthesized using a seed mediated hot injection method, and monodispersed Fe3O4 (4 nm) nanoparticles were prepared from iron(II) actylacetonate by a precursor thermal decomposition method. Structural and morphology verified NaYF4:Yb:Er:Tm@NaGdF4 and Fe3O4 nanoparticles were utilized for the preparation of NaYF4:Yb:Er:Tm@NaGdF4/Fe3O4@SiO2 nanocomposite using a micro-emulsion method. Existence of Fe3O4 in NaYF4:Yb:Er:Tm@NaGdF4 in SiO2 nano-spheres were confirmed with transmission electron microscopy. Luminescence measurement revealed that NaYF4:Yb:Er:Tm@NaGdF4 exhibited strong emissions at green and red regions, in addition to a weak blue emission also observed under 980 nm excitation. Up-conversion emission of the nanoparticle-embedded silica nanocomposite showed that the up-conversion emission was not affected by Fe3O4 nanoparticles.

A Highly Efficient UV-Vis-NIR Active Ln(3+)-Doped BiPO4/BiVO4 Nanocomposite for Photocatalysis Application.

PubMed

Ganguli, Sagar; Hazra, Chanchal; Chatti, Manjunath; Samanta, Tuhin; Mahalingam, Venkataramanan

2016-01-12

In this Article, we report the synthesis of Ln(3+) (Yb(3+), Tm(3+))-doped BiPO4/BiVO4 nanocomposite photocatalyst that shows efficient photocatalytic activity under UV-visible-near-infrared (UV-vis-NIR) illumination. Incorporation of upconverting Ln(3+) ion pairs in BiPO4 nanocrystals resulted in strong emission in the visible region upon excitation with a NIR laser (980 nm). A composite of BiPO4 nanocrystals and vanadate was prepared by the addition of vanadate source to BiPO4 nanocrystals. In the nanocomposite, the strong blue emission from Tm(3+) ions via upconversion is nonradiatively transferred to BiVO4, resulting in the production of excitons. This in turn generates reactive oxygen species and efficiently degrades methylene blue dye in aqueous medium. The nanocomposite also shows high photocatalytic activity both under the visible region (0.010 min(-1)) and under the full solar spectrum (0.047 min(-1)). The results suggest that the photocatalytic activity of the nanocomposite under both NIR as well as full solar irradiation is better compared to other reported nanocomposite photocatalysts. The choice of BiPO4 as the matrix for Ln(3+) ions has been discussed in detail, as it plays an important role in the superior NIR photocatalytic activity of the nanocomposite photocatalyst.

Advances in spectral conversion for photovoltaics: up-converting Er3+ doped YF3 nano-crystals in transparent glass ceramic

NASA Astrophysics Data System (ADS)

Marques-Hueso, Jose; Chen, Daqin; MacDougall, Sean K. W.; Wang, Yuansheng; Richards, Bryce S.

2011-09-01

Up- and down-conversion (UC, DC) constitute two singular routes to achieve improved energy harvesting of sunlight by changing its shape of the solar spectrum. To obtain a significant conversion rate two main challenges have to be overcome: i) the excited lanthanide ions have to emit efficiently, a target which has been better accomplished for DC materials; ii) the absorption in the lanthanide-based UC and DC layers has to be high to ensure a sizeable fraction of photons can be harvested. In this paper, we review such materials and their use as spectral converters for photovoltaics (PV), paying special attention to the UC and DC processes in lanthanide glasses in fluoride matrices. We discuss the challenges that need to be overcome in order to implement these materials in real PV devices. Finally, we will present the synthesis of erbium (Er3+) doped YF3 nano-crystals embedded in transparent glass ceramic (TGC) by melt quenching. This material presents a low phonon energy environment for the Er3+ ions due to the fluoride crystals, while the silica glass provides chemical and mechanical stability to the compound.

Synthesis of NaYF4:Yb/Er/Gd up-conversion luminescent nanoparticles and luminescence resonance energy transfer-based protein detection

PubMed Central

Zhang, Jingpu; Mi, Congcong; Wu, Hongyan; Huang, Huaiqing; Mao, Chuanbin; Xu, Shukun

2012-01-01

High-quality NaYF4:Yb/Er/Gd up-conversion nanoparticles (UCNPs) were first synthesized by a solvothermal method using rare earth stearate, sodium fluoride, ethanol, water, and oleic acid as precursors. Doped Gd3+ ions can promote the transition of NaYF4 from cubic to hexagonal phase, shorten the reaction time, and reduce the reaction temperature without reducing the luminescence intensity of NaYF4:Yb/Er UCNPs. X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and luminescence spectroscopy were applied to characterize the UCNPs. The nanoparticles exhibited small size and excellent green up-conversion photoluminescence, making them suitable for biological applications. After the surfaces of NaYF4:Yb/Er/Gd UCNPs were modified with amino groups through the Stöber method, they could be brought close enough to the analytically important protein called R-phycoerythrin (R-PE) bearing multiple carboxyl groups so that energy transfer could occur. A luminescence resonance energy transfer (LRET) system was developed using NaYF4:Yb/Er/Gd UCNPs as an energy donor and R-PE as an energy acceptor. As a result, a detection limit of R-PE of 0.5 μg/ml was achieved by the LRET system with a relative standard deviation of 2.0%. Although this approach was first used successfully to detect R-PE, it can also be extended to the detection of other biological molecules. PMID:22155069

Modifying the size and uniformity of upconversion Yb/Er:NaGdF4 nanocrystals through alkaline-earth doping.

PubMed

Lei, Lei; Chen, Daqin; Huang, Ping; Xu, Ju; Zhang, Rui; Wang, Yuansheng

2013-11-21

NaGdF4 is regarded as an ideal upconversion (UC) host material for lanthanide (Ln(3+)) activators because of its unique crystal structure, high Ln(3+) solubility, low phonon energy and high photochemical stability, and Ln(3+)-doped NaGdF4 UC nanocrystals (NCs) have been widely investigated as bio-imaging and magnetic resonance imaging agents recently. To realize their practical applications, controlling the size and uniformity of the monodisperse Ln(3+)-doped NaGdF4 UC NCs is highly desired. Unlike the routine routes by finely adjusting the multiple experimental parameters, herein we provide a facile and straightforward strategy to modify the size and uniformity of NaGdF4 NCs via alkaline-earth doping for the first time. With the increase of alkaline-earth doping content, the size of NaGdF4 NCs increases gradually, while the size-uniformity is still retained. We attribute this "focusing" of size distribution to the diffusion controlled growth of NaGdF4 NCs induced by alkaline-earth doping. Importantly, adopting the Ca(2+)-doped Yb/Er:NaGdF4 NCs as cores, the complete Ca/Yb/Er:NaGdF4@NaYF4 core-shell particles with excellent size-uniformity can be easily achieved. However, when taking the Yb/Er:NaGdF4 NCs without Ca(2+) doping as cores, they could not be perfectly covered by NaYF4 shells, and the obtained products are non-uniform in size. As a result, the UC emission intensity of the complete core-shell NCs increases by about 30 times in comparison with that of the cores, owing to the effective surface passivation of the Ca(2+)-doped cores and therefore protection of Er(3+) in the cores from the non-radiative decay caused by surface defects, whereas the UC intensity of the incomplete core-shell NCs is enhanced by only 3 times.

Photoluminescence of transparent glass-ceramics based on ZnO nanocrystals and co-doped with Eu3+, Yb3+ ions

NASA Astrophysics Data System (ADS)

Arzumanyan, Grigory M.; Kuznetsov, Evgeny A.; Zhilin, Aleksandr A.; Dymshits, Olga S.; Shemchuk, Daria V.; Alekseeva, Irina P.; Mudryi, Alexandr V.; Zhivulko, Vadim D.; Borodavchenko, Olga M.

2016-12-01

Glasses of the K2Osbnd ZnOsbnd Al2O3sbnd SiO2 system co-doped with Eu2O3 and Yb2O3 were prepared by the melt-quenching technique. Transparent zincite (ZnO) glass-ceramics were obtained by secondary heat-treatments at 680-860 °C. At 860 °C, traces of Eu oxyapatite appeared in addition to ZnO nanocrystals. The average crystal size obtained from the X-ray diffraction data was found to range between 14 and 35 nm. Absorption spectra of the initial glasses are composed of an absorption edge and absorption bands due to electronic transitions of Eu3+ ions. With heat-treatment, the absorption edge pronouncedly shifts to the visible spectral range. The luminescence properties of the glass and glass-ceramics were studied by measuring their excitation and emission spectra at 300, 78, and 4.2 K. Strong red emission of Eu3+ ions dominated by the 5D0-7F2 (612 nm) electric dipole transition was detected. Changes in the luminescence properties of the Eu3+-related excitation and emission bands were observed after heat-treatments at 680 °C and 860 °C. The ZnO nanocrystals showed both broad luminescence (400-850 nm) and free-exciton emission near 3.3 eV at room temperature. The upconversion luminescence spectrum of the initial glass was obtained under excitation of the 976 nm laser source.

Tuning into single-band red upconversion luminescence in Yb(3+)/Ho(3+) activated nano-glass-ceramics through Ce(3+) doping.

PubMed

Chen, Daqin; Zhou, Yang; Wan, Zhongyi; Ji, Zhenguo; Huang, Ping

2015-03-28

Yb(3+)/Ho(3+) activated glass ceramics containing β-YF3 nanocrystals were successfully fabricated. The green ((5)S2/(5)F4→(5)I8) upconversion emission is dominant in the glass ceramics and is about 160 times stronger than that of the precursor glass, resulting from the partition of lanthanide activators into a low-phonon-energy crystalline lattice and the subsequent low probability of multi-phonon nonradiative relaxation from the (5)S2/(5)F4 and (5)I6 states to the lower ones. Upon the introduction of Ce(3+) ions into nano-glass-ceramics, two efficient cross-relaxation processes between Ho(3+) and Ce(3+), i.e., Ho(3+):(5)S2/(5)F4 + Ce(3+):(2)F5/2→Ho(3+):(5)F5 + Ce(3+):(2)F7/2 and Ho(3+):(5)I6 + Ce(3+):(2)F5/2→Ho(3+):(5)I7 + Ce(3+):(2)F7/2, are demonstrated to greatly suppress the population of the green-emitting (5)S2/(5)F4 state and to enhance the population of the red-emitting (5)F5 one, leading to the intense single-band red UC radiation of Ho(3+).

Core - shell upconversion nanoparticle - semiconductor heterostructures for photodynamic therapy

NASA Astrophysics Data System (ADS)

Dou, Qing Qing; Rengaramchandran, Adith; Selvan, Subramanian Tamil; Paulmurugan, Ramasamy; Zhang, Yong

2015-02-01

Core-shell nanoparticles (CSNPs) with diverse chemical compositions have been attracting greater attention in recent years. However, it has been a challenge to develop CSNPs with different crystal structures due to the lattice mismatch of the nanocrystals. Here we report a rational design of core-shell heterostructure consisting of NaYF4:Yb,Tm upconversion nanoparticle (UCN) as the core and ZnO semiconductor as the shell for potential application in photodynamic therapy (PDT). The core-shell architecture (confirmed by TEM and STEM) enables for improving the loading efficiency of photosensitizer (ZnO) as the semiconductor is directly coated on the UCN core. Importantly, UCN acts as a transducer to sensitize ZnO and trigger the generation of cytotoxic reactive oxygen species (ROS) to induce cancer cell death. We also present a firefly luciferase (FLuc) reporter gene based molecular biosensor (ARE-FLuc) to measure the antioxidant signaling response activated in cells during the release of ROS in response to the exposure of CSNPs under 980 nm NIR light. The breast cancer cells (MDA-MB-231 and 4T1) exposed to CSNPs showed significant release of ROS as measured by aminophenyl fluorescein (APF) and ARE-FLuc luciferase assays, and ~45% cancer cell death as measured by MTT assay, when illuminated with 980 nm NIR light.

Synthesis and the luminescent properties of the Nd3+ ions doped three kinds of fluoride nanocrystals in organic solvents

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Tian, Changyong; Bo, Shuhui; Liu, Xinhou; Zhen, Zhen

2015-10-01

Oleic acid (OA)-modified LaF3:Nd, NaYF4:Nd and CaF2:Nd nanocrystals (NCs) with the different Nd3+ ion concentration (2% and 5%) have been prepared. The structure and morphology of NCs were identified by XRD, TEM, FT-IR and TGA. The size of OA-modified NC is a mean diameter of 5-10 nm and can be dispersed in common organic solvents to form a transparent solution. The optical loss of NCs in organic solvent is the first time to discuss in this work. The luminescence properties of NCs were also characterized and studied by fluorescence spectrometer. The nanoparticles in solid and in the solution all exhibited the strong emission at the 1060 nm when the materials were excited around 800 nm. Compared with the LaF3 and CaF2 matrix, NaYF4 as the host can protect the Nd3+ ions more efficiently away from the nonradiative transitions. The longest luminescent lifetime of the solid NaYF4:2%Nd NCs was up to 136 μs, and the little difference of the fluorescence lifetime existed between the NCs in solid state and in solution. The low optical loss in organic solvent indicated that the Nd3+ ions-doped fluoride NCs are promising materials for optical amplification fields.

Survey and research on up-conversion emission character and energy transition of Yb3+/Er3+/Tm3+ co-doped phosphate glass and glass ceramic

NASA Astrophysics Data System (ADS)

Yu, Yin; Song, Feng; Ming, Chengguo; Liu, Jiadong; Li, Wei; Liu, Yanling; Zhao, Hongyan

2012-11-01

By conventional high-temperature melting method, Yb3+/Er3+/Tm3+ co-doped phosphate glass was synthesized. After annealing the precursor glass, the phosphate glass ceramic (GC) was obtained. By measuring the X-ray diffraction (XRD) spectrum, it is proved that the LiYbP4O12 and Li6P6O18 nano-crystals have existed in the phosphate GC. The up-conversion (UC) emission intensity of the GC is obvious stronger compared to that of the glass. The reason is that the shorter distance between rare earth ions in the glass ceramic increases the energy transitions from the sensitized ions (Yb3+) to the luminous ions (Er3+ and Tm3+). By studying the dependence of UC emissions on the pump power, the 523 and 546 nm green emissions of Er3+ ions in the glass are two-photon processes. But in the glass ceramic, they are two/three-photon processes. The phenomenon implies that a three-photon process has participated in the population of the two green emissions. Using Dexter theory, we discuss the energy transitions of Er3+ and Tm3+. The results indicate the energy transition of Tm3+ to Er3+ is very strong in the GC, which changes the population mechanism of UC emissions of Er3+.

Paramagnetic Nanocrystals: Remarkable Lanthanide-Doped Nanoparticles with Varied Shape, Size, and Composition.

PubMed

Holmberg, Rebecca J; Aharen, Tomoko; Murugesu, Muralee

2012-12-20

Magnetic nanoparticles have been developed in recent years with applications in unique and crucial areas such as biomedicine, data storage, environmental remediation, catalysis, and so forth. NaYF4 nanoparticles were synthesized and isolated with lanthanide dopant percentages, confirmed by ICP-OES measurements, of Er, Yb, Tb, Gd, and Dy that were in agreement with the targeted ratios. SEM images showed a distinct variation in particle size and shape with dopant type and percentage. HRTEM and XRD studies confirmed the particles to be crystalline, possessing both α and β phases. Magnetic measurements determined that all of the nanoparticles were paramagnetic and did not exhibit a blocking temperature from 2 to 300 K. The multifunctional properties of these nanoparticles make them suitable for many applications, such as multimodal imaging probes, up-conversion fluorescent markers, as well as MRI contrast agents.

Luminescence Properties of Surface Radiation-Induced Defects in Lithium Fluoride

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Martynovich, E. F.; Novikov, A. N.; Runets, L. P.; Stupak, A. P.

2013-11-01

Luminescence and luminescence excitation spectra are recorded for surface radiation-induced defects in lithium fluoride at temperatures of 77 and 293 K. The presence of three bands with relatively small intensity differences is a distinctive feature of the excitation spectrum. These bands are found to belong to the same type of defects. The positions of the peaks and the widths of the absorption and luminescence bands for these defects are determined. The luminescence decay time is measured. All the measured characteristics of these surface defects differ from those of previously known defects induced by radiation in the bulk of the crystals. It is found that the luminescence of surface defects in an ensemble of nanocrystals with different orientations is not polarized. The number of anion vacancies in the surface defects is estimated using the polarization measurements. It is shown that radiative scattering distorts the intensity ratios of the luminescence excitation bands located in different spectral regions.

Synergistically Enhanced Performance of Ultrathin Nanostructured Silicon Solar Cells Embedded in Plasmonically Assisted, Multispectral Luminescent Waveguides.

PubMed

Lee, Sung-Min; Dhar, Purnim; Chen, Huandong; Montenegro, Angelo; Liaw, Lauren; Kang, Dongseok; Gai, Boju; Benderskii, Alexander V; Yoon, Jongseung

2017-04-25

Ultrathin silicon solar cells fabricated by anisotropic wet chemical etching of single-crystalline wafer materials represent an attractive materials platform that could provide many advantages for realizing high-performance, low-cost photovoltaics. However, their intrinsically limited photovoltaic performance arising from insufficient absorption of low-energy photons demands careful design of light management to maximize the efficiency and preserve the cost-effectiveness of solar cells. Herein we present an integrated flexible solar module of ultrathin, nanostructured silicon solar cells capable of simultaneously exploiting spectral upconversion and downshifting in conjunction with multispectral luminescent waveguides and a nanostructured plasmonic reflector to compensate for their weak optical absorption and enhance their performance. The 8 μm-thick silicon solar cells incorporating a hexagonally periodic nanostructured surface relief are surface-embedded in layered multispectral luminescent media containing organic dyes and NaYF 4 :Yb 3+ ,Er 3+ nanocrystals as downshifting and upconverting luminophores, respectively, via printing-enabled deterministic materials assembly. The ultrathin nanostructured silicon microcells in the composite luminescent waveguide exhibit strongly augmented photocurrent (∼40.1 mA/cm 2 ) and energy conversion efficiency (∼12.8%) than devices with only a single type of luminescent species, owing to the synergistic contributions from optical downshifting, plasmonically enhanced upconversion, and waveguided photon flux for optical concentration, where the short-circuit current density increased by ∼13.6 mA/cm 2 compared with microcells in a nonluminescent medium on a plain silver reflector under a confined illumination.

Photon upconversion in homogeneous fluorescence-based bioanalytical assays.

PubMed

Soukka, Tero; Rantanen, Terhi; Kuningas, Katri

2008-01-01

Upconverting phosphors (UCPs) are very attractive reporters for fluorescence resonance energy transfer (FRET)-based bioanalytical assays. The large anti-Stokes shift and capability to convert near-infrared to visible light via sequential absorption of multiple photons enable complete elimination of autofluorescence, which commonly impairs the performance of fluorescence-based assays. UCPs are ideal donors for FRET, because their very narrow-banded emission allows measurement of the sensitized acceptor emission, in principle, without any crosstalk from the donor emission at a wavelength just tens of nanometers from the emission peak of the donor. In addition, acceptor dyes emitting at visible wavelengths are essentially not excited by near-infrared, which further emphasizes the unique potential of upconversion FRET (UC-FRET). These characteristics result in favorable assay performance using detection instrumentation based on epifluorometer configuration and laser diode excitation. Although UC-FRET is a recently emerged technology, it has already been applied in both immunoassays and nucleic acid hybridization assays. The technology is also compatible with optically difficult biological samples, such as whole blood. Significant advances in assay performance are expected using upconverting lanthanide-doped nanocrystals, which are currently under extensive research. UC-FRET, similarly to other fluorescence techniques based on resonance energy transfer, is strongly distance dependent and may have limited applicability, for example in sandwich-type assays for large biomolecules, such as viruses. In this article, we summarize the essentials of UC-FRET, describe its current applications, and outline the expectations for its future potential.

Synergistically Enhanced Performance of Ultrathin Nanostructured Silicon Solar Cells Embedded in Plasmonically Assisted, Multispectral Luminescent Waveguides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sung-Min; Dhar, Purnim; Chen, Huandong

Ultrathin silicon solar cells fabricated by anisotropic wet chemical etching of single-crystalline wafer materials represent an attractive materials platform that could provide many advantages for realizing high-performance, low-cost photovoltaics. However, their intrinsically limited photovoltaic performance arising from insufficient absorption of low-energy photons demands careful design of light management to maximize the efficiency and preserve the cost-effectiveness of solar cells. Herein we present an integrated flexible solar module of ultrathin, nanostructured silicon solar cells capable of simultaneously exploiting spectral upconversion and downshifting in conjunction with multispectral luminescent waveguides and a nanostructured plasmonic reflector to compensate for their weak optical absorption andmore » enhance their performance. The 8 μm-thick silicon solar cells incorporating a hexagonally periodic nanostructured surface relief are surface-embedded in layered multispectral luminescent media containing organic dyes and NaYF4:Yb3+,Er3+ nanocrystals as downshifting and upconverting luminophores, respectively, via printing-enabled deterministic materials assembly. The ultrathin nanostructured silicon microcells in the composite luminescent waveguide exhibit strongly augmented photocurrent (~40.1 mA/cm2) and energy conversion efficiency (~12.8%) than devices with only a single type of luminescent species, owing to the synergistic contributions from optical downshifting, plasmonically enhanced upconversion, and waveguided photon flux for optical concentration, where the short-circuit current density increased by ~13.6 mA/cm2 compared with microcells in a nonluminescent medium on a plain silver reflector under a confined illumination.« less

Optimizing the Activation of Chlorin e6 Utilizing Upconversion Energy Transfer

NASA Astrophysics Data System (ADS)

Avalos, Julio C.; Pedraza, Francisco J.; Sardar, Dhiraj K.

2015-03-01

Current cancer therapy techniques, such as chemotherapy and radiation therapy, possess several drawbacks including lack of selectivity resulting in harmful side effects. Photodynamic therapy (PDT) is one of the fastest emerging techniques due to its many advantages, including the use of nonionizing radiation, targeted delivery, and controlled doses. In PDT, photosensitizers (PSs) are activated inside targeted cells to produce irreversible damage inducing cell death. Since most PSs operate in the visible range, it is difficult to activate them due to the high attenuation of soft tissue. Upconverting nanoparticles (UCNP) are able to absorb in the NIR region, where light is less attenuated, and emit in the visible range, resulting in deeper tissue penetration. UCNPs are able to assist with the activation of the PS by energy transfer when the PS is conjugated onto the UCNP. Chlorin e6 (Ce6) is a commonly used PSs due to its ability to release reactive oxygen species (ROS), which is one of the main processes utilized in PDT. The UCNP studied contain a combination of rare earth doped ions including Erbium, Thulium, and Holmium precisely doped into the host nanocrystal to improve upconversion emission and energy transfer. The work presented will focus on exploring the factors that affect the activation of Ce6. The results will include the enhancement of Ce6 activation and ROS release when conjugated onto a rare earth-doped UCNP. This research was funded by NSF-PREM Grant No. DMR -0934218 and RISE Grant No. GM 060655.

High-efficiency near-infrared enabled planar perovskite solar cells by embedding upconversion nanocrystals.

PubMed

Meng, Fan-Li; Wu, Jiao-Jiao; Zhao, Er-Fei; Zheng, Yan-Zhen; Huang, Mei-Lan; Dai, Li-Ming; Tao, Xia; Chen, Jian-Feng

2017-11-30

Integration of the upconversion effect in perovskite solar cells (PSCs) is a facile approach towards extending the spectral absorption from the visible to the near infrared (NIR) range and reducing the non-absorption loss of solar photons. However, the big challenge for practical application of UCNCs in planar PSCs is the poor compatibility between UCNCs and the perovskite precursor. Herein, we have subtly overcome the tough compatibility issue using a ligand-exchange strategy. For the first time, β-NaYF 4 :Yb,Er UCNCs have been embedded in situ into a CH 3 NH 3 PbI 3 layer to fabricate NIR-enabled planar PSCs. The CH 3 NH 3 I-capped UCNCs generated from the ligand-exchange were mixed with the perovskite precursor and served as nucleation sites for the UCNC-mediated heteroepitaxial growth of perovskite; moreover, the in situ embedding of UCNCs into the perovskite layer was realized during a spin-coating process. The resulting UCNC-embedded perovskite layer attained a uniform pinhole-free morphology with enlarged crystal grains and enabled NIR absorption. It also contributed to the energy transfer from the UCNCs to the perovskite and electron transport to the collecting electrode surface. The device fabricated using the UCNC-embedded perovskite film achieved an average power-conversion efficiency of 18.60% (19.70% for the best) under AM 1.5G and 0.37% under 980 nm laser, corresponding to 54% and 740-fold increase as compared to that of its counterpart without UCNCs.

Porous microwells for geometry-selective, large-scale microparticle arrays

NASA Astrophysics Data System (ADS)

Kim, Jae Jung; Bong, Ki Wan; Reátegui, Eduardo; Irimia, Daniel; Doyle, Patrick S.

2017-01-01

Large-scale microparticle arrays (LSMAs) are key for material science and bioengineering applications. However, previous approaches suffer from trade-offs between scalability, precision, specificity and versatility. Here, we present a porous microwell-based approach to create large-scale microparticle arrays with complex motifs. Microparticles are guided to and pushed into microwells by fluid flow through small open pores at the bottom of the porous well arrays. A scaling theory allows for the rational design of LSMAs to sort and array particles on the basis of their size, shape, or modulus. Sequential particle assembly allows for proximal and nested particle arrangements, as well as particle recollection and pattern transfer. We demonstrate the capabilities of the approach by means of three applications: high-throughput single-cell arrays; microenvironment fabrication for neutrophil chemotaxis; and complex, covert tags by the transfer of an upconversion nanocrystal-laden LSMA.

Demonstration of Temperature Dependent Energy Migration in Dual-Mode YVO4: Ho3+/Yb3+ Nanocrystals for Low Temperature Thermometry

PubMed Central

Kumar Mahata, Manoj; Koppe, Tristan; Kumar, Kaushal; Hofsäss, Hans; Vetter, Ulrich

2016-01-01

A dual mode rare-earth based vanadate material (YVO4: Ho3+/Yb3+), prepared through ethylene glycol assisted hydrothermal method, demonstrating both downconversion and upconversion, along with systematic investigation of the luminescence spectroscopy within 12–300 K is presented herein. The energy transfer processes have been explored via steady-state and time-resolved spectroscopic measurements and explained in terms of rate equation description and temporal evolution below room temperature. The maximum time for energy migration from host to rare earth (Ho3+) increases (0.157 μs to 0.514 μs) with the material’s temperature decreasing from 300 K to 12 K. The mechanism responsible for variation of the transients’ character is discussed through thermalization and non-radiative transitions in the system. More significantly, the temperature of the nanocrystals was determined using not only the thermally equilibrated radiative intra-4f transitions of Ho3+ but also the decay time and rise time of vanadate and Ho3+ energy levels. Our studies show that the material is highly suitable for temperature sensing below room temperature. The maximum relative sensor sensitivity using the rise time of Ho3+ energy level (5F4/5S2) is 1.35% K−1, which is the highest among the known sensitivities for luminescence based thermal probes. PMID:27805060

Improvement of antifouling performances for modified PVDF ultrafiltration membrane with hydrophilic cellulose nanocrystal

NASA Astrophysics Data System (ADS)

Lv, Jinling; Zhang, Guoquan; Zhang, Hanmin; Zhao, Chuanqi; Yang, Fenglin

2018-05-01

Hydrophilic cellulose nanocrystal (CNC) was incorporated into hydrophobic poly(vinylidene fluoride) (PVDF) membrane via phase inversion process to improve membrane antifouling property. The effects of CNC on membrane morphology, hydrophilicity, permeability and antifouling property were investigated in-detail. Results indicated that the introduction of CNC into PVDF membrane enhanced the permeability by optimizing membrane microstructure and improving membrane hydrophilicity. A higher pure water flux of 206.9 L m-2 h-1 was achieved for CNC/PVDF membrane at 100 kPa, which was 20 times that of PVDF membrane (9.8 L m-2 h-1). In bovine serum albumin filtration measurements, the permeation flux and flux recovery ratio of CNC/PVDF membrane were increased remarkably, while the irreversible fouling-resistance of CNC/PVDF membrane decreased by 48.8%. These results indicated that the CNC/PVDF membrane possessed superior antifouling property due to the hydrophilicity of CNC that formed a hydration layer on the membrane surface to effectively reduce contaminants adsorption/deposition.

Growth and characterization of spindle-like Ga2O3 nanocrystals by electrochemical reaction in hydrofluoric solution

NASA Astrophysics Data System (ADS)

Feng, Lungang; Li, Yufeng; Su, Xilin; Wang, Shuai; Liu, Hao; Wang, Jiangteng; Gong, Zhina; Ding, Wen; Zhang, Ye; Yun, Feng

2016-12-01

We report a novel fabrication method of spindle-like gallium oxide (Ga2O3) nanocrystals via two steps processed by electrochemical reaction of the MOVPE-grown GaN epitaxial layer in HF/ethanol (1:6) electrolyte and subsequent heat treatment. Depending on the electrolyte concentration, reaction time and applied voltage, micrometer- to nanometer-size spindle-like gallium fluoride tri-hydrate (GaF3·3H2O) of different densities and geometrical dimensions were formed on the surface of GaN. EDS, XPS and XRD were used to characterize the properties of the material before and after heat treatment. It is found that due to heat treatment at above 600 °C, nanocrystalline Ga2O3 were transformed from the GaF3·3H2O via pyrohydrolysis reaction mechanism. The band gap of ∼5.1 eV of the spindle-like Ga2O3 was measured by the optical absorption spectroscopy.

Giant enhancement of upconversion in ultra-small Er³⁺/Yb³⁺:NaYF₄ nanoparticles via laser annealing.

PubMed

Bednarkiewicz, A; Wawrzynczyk, D; Gagor, A; Kepinski, L; Kurnatowska, M; Krajczyk, L; Nyk, M; Samoc, M; Strek, W

2012-04-13

Most of the synthesis routes of lanthanide-doped phosphors involve thermal processing which results in nanocrystallite growth, stabilization of the crystal structure and augmentation of luminescence intensity. It is of great interest to be able to transform the sample in a spatially localized manner, which may lead to many applications like 2D and 3D data storage, anti-counterfeiting protection, novel design bio-sensors and, potentially, to fabrication of metamaterials, 3D photonic crystals or plasmonic devices. Here we demonstrate irreversible spatially confined infrared-laser-induced annealing (LIA) achieved in a thin layer of dried colloidal solution of ultra-small ∼8 nm NaYF₄ nanocrystals (NCs) co-doped with 2% Er³⁺ and 20% Yb³⁺ ions under a localized tightly focused beam from a continuous wave 976 nm medium power laser diode excitation. The LIA results from self-heating due to non-radiative relaxation accompanying the NIR laser energy upconversion in lanthanide ions. We notice that localized LIA appears at optical power densities as low as 15.5 kW cm⁻² (∼354 ± 29 mW) threshold in spots of 54 ± 3 µm diameter obtained with a 10 × microscope objective. In the course of detailed studies, a complete recrystallization to different phases and giant 2-3 order enhancement in luminescence yield is found. Our results are highly encouraging and let us conclude that the upconverting ultra-small lanthanide-doped nanophosphors are particularly promising for direct laser writing applications.

Giant enhancement of upconversion in ultra-small Er3+/Yb3+:NaYF4 nanoparticles via laser annealing

NASA Astrophysics Data System (ADS)

Bednarkiewicz, A.; Wawrzynczyk, D.; Gagor, A.; Kepinski, L.; Kurnatowska, M.; Krajczyk, L.; Nyk, M.; Samoc, M.; Strek, W.

2012-04-01

Most of the synthesis routes of lanthanide-doped phosphors involve thermal processing which results in nanocrystallite growth, stabilization of the crystal structure and augmentation of luminescence intensity. It is of great interest to be able to transform the sample in a spatially localized manner, which may lead to many applications like 2D and 3D data storage, anti-counterfeiting protection, novel design bio-sensors and, potentially, to fabrication of metamaterials, 3D photonic crystals or plasmonic devices. Here we demonstrate irreversible spatially confined infrared-laser-induced annealing (LIA) achieved in a thin layer of dried colloidal solution of ultra-small ˜8 nm NaYF4 nanocrystals (NCs) co-doped with 2% Er3+ and 20% Yb3+ ions under a localized tightly focused beam from a continuous wave 976 nm medium power laser diode excitation. The LIA results from self-heating due to non-radiative relaxation accompanying the NIR laser energy upconversion in lanthanide ions. We notice that localized LIA appears at optical power densities as low as 15.5 kW cm-2 (˜354 ± 29 mW) threshold in spots of 54 ± 3 µm diameter obtained with a 10 × microscope objective. In the course of detailed studies, a complete recrystallization to different phases and giant 2-3 order enhancement in luminescence yield is found. Our results are highly encouraging and let us conclude that the upconverting ultra-small lanthanide-doped nanophosphors are particularly promising for direct laser writing applications.

Solvothermal synthesis and surface chemistry to control the size and morphology of nanoquartz

DOE PAGES

Sochalski-Kolbus, Lindsay M.; Wang, Hsiu-Wen; Rondinone, Adam Justin; ...

2015-09-29

In this paper, we report a solvothermal synthesis method that allows the crystallization of quartz to occur at a relatively low temperature of 300°C in the form of isolated nanosized euhedral crystals. Transmission electron microscopy (TEM) and small area electron diffraction (SAED) were used to confirm the phases present and their particle sizes, morphologies, and crystallinity of the products. In conclusion, the results show that it is possible to control the size and morphology of the nanoquartz from rough nanospheres to nanorods using fluoride, which templates the nanocrystals and moderates growth.

Lanthanum fluoride nanoparticles for radiosensitization of tumors

NASA Astrophysics Data System (ADS)

Kudinov, Konstantin; Bekah, Devesh; Cooper, Daniel; Shastry, Sathvik; Hill, Colin; Bradforth, Stephen; Nadeau, Jay

2016-03-01

Dense inorganic nanoparticles have recently been identified as promising radiosensitizers. In addition to dose enhancement through increased attenuation of ionizing radiation relative to biological tissue, scintillating nanoparticles can transfer energy to coupled photosensitizers to amplify production of reactive oxygen species, as well as provide UVvisible emission for optical imaging. Lanthanum fluoride is a transparent material that is easily prepared as nanocrystals, and which can provide radioluminescence at a number of wavelengths through simple substitution of lanthanum ions with other luminescent lanthanides. We have prepared lanthanum fluoride nanoparticles doped with cerium, terbium, or both, that have good spectral overlap with chlorine6 or Rose Bengal photosensitizer molecules. We have also developed a strategy for stable conjugation of the photosensitizers to the nanoparticle surface, allowing for high energy transfer efficiencies on a per molecule basis. Additionally, we have succeeded in making our conjugates colloidally stable under physiological conditions. Here we present our latest results, using nanoparticles and nanoparticle-photosensitizer conjugates to demonstrate radiation dose enhancement in B16 melanoma cells. The effects of nanoparticle treatment prior to 250 kVp x-ray irradiation were investigated through clonogenic survival assays and cell cycle analysis. Using a custom apparatus, we have also observed scintillation of the nanoparticles and conjugates under the same conditions that the cell samples are irradiated.

Mechanisms and concentrations dependence of up-conversion luminescence in Tm^3^+/Yb^3^+ codoped oxyfluoride glass-ceramics [rapid communication

NASA Astrophysics Data System (ADS)

Zhang, Junjie; He, Dongbing; Duan, Zhongchao; Zhang, Liyan; Dai, Shixun; Hu, Lili

2005-04-01

The up-conversion properties of Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation were investigated. Intense blue up-conversion luminescence due to the Tm3+: 1G4 → 3H6 transition was observed in the glass-ceramics. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The up-conversion mechanism is proposed. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics and the concentrations dependence of upconversion luminescence are also discussed.

Trivalent rare-earth activated hexagonal lanthanum fluoride (LaF3 :RE3+ , where RE = Tb, Sm, Dy and Tm) nanocrystals: Synthesis and optical properties.

PubMed

Kasturi, Singh; Marikumar, R; Vaidyanathan, Sivakumar

2018-05-10

The LaF 3 nanocrystals through a facile hydrothermal route with hexagonal structures have been synthesized via doping of trivalent rare earth (RE 3+ ) ions - RE = Tb, Sm, Dy and Tm - with rod-like and perforated morphologies using NH 4 F as fluorine precursor. Hexagonal phase formation was confirmed by powder X-ray diffraction. The crystalline sizes were calculated by the Scherrer equation where found to have an average crystalline size of 12 to 35 nm. The morphological studies of the nanocrystals were carried out by means of transmission electron microscopy (TEM). The LaF 3 :Tm 3+ ,Sm 3+ ions show the characteristic emission of Tb 3+ and Tm 3+ respectively. In Sm 3+ -doped LaF 3 , three prominent emission peaks at 561, 597 and 641 nm were found, which belong to 4 G 5/2  →  6 H 5/2 , 4 G 5/2  →  6 H 7/2 (magnetic dipole) and 4 G 5/2  →  6 H 9/2 (electric dipole) transitions, respectively. The Dy 3+ activated LaF 3 shows blue and yellow emission and the corresponding CIE color coordinate show white light emission (CCT value 10650 K). Copyright © 2018 John Wiley & Sons, Ltd.

Up-conversion in rare-earth doped micro-particles applied to new emissive two-dimensional displays

NASA Astrophysics Data System (ADS)

Milliez, Anne Janet

Up-conversion (UC) in rare-earth co-doped fluorides to convert diode laser light in the near infrared to red, green and blue visible light is applied to make possible high performance emissive displays. The infrared-to-visible UC in the materials we study is a sequential form of non-linear two photon absorption in which a strong absorbing constituent absorbs two low energy photons and transfers this energy to another constituent which emits visible light. Some of the UC emitters' most appealing characteristics for displays are: a wide color gamut with very saturated colors, very high brightness operation without damage to the emitters, long lifetimes and efficiencies comparable to those of existing technologies. Other advantages include simplicity of fabrication, versatility of operating modes, and the potential for greatly reduced display weight and depth. Thanks to recent advances in material science and diode laser technology at the excitation wavelength, UC selected materials can be very efficient visible emitters. However, optimal UC efficiencies strongly depend on chosing proper operating conditions. In this thesis, we studied the conditions required for optimization. We demonstrated that high efficiency UC depends on high pump irradiance, low temperature and low scattering. With this understanding we can predict how to optimally use UC emitters in a wide range of applications. In particular, we showed how our very efficient UC emitters can be applied to make full color displays and very efficient white light sources.

Modular Integration of Upconverting Nanocrystal-Dendrimer Composites for Folate Receptor-Specific NIR Imaging and Light-Triggered Drug Release.

PubMed

Wong, Pamela T; Chen, Dexin; Tang, Shengzhuang; Yanik, Sean; Payne, Michael; Mukherjee, Jhindan; Coulter, Alexa; Tang, Kenny; Tao, Ke; Sun, Kang; Baker, James R; Choi, Seok Ki

2015-12-02

Upconversion nanocrystals (UCNs) display near-infrared (NIR)-responsive photoluminescent properties for NIR imaging and drug delivery. The development of effective strategies for UCN integration with other complementary nanostructures for targeting and drug conjugation is highly desirable. This study reports on a core/shell-based theranostic system designed by UCN integration with a folate (FA)-conjugated dendrimer for tumor targeting and with photocaged doxorubicin as a cytotoxic agent. Two types of UCNs (NaYF4:Yb/Er (or Yb/Tm); diameter = ≈50 to 54 nm) are described, each displaying distinct emission properties upon NIR (980 nm) excitation. The UCNs are surface modified through covalent attachment of photocaged doxorubicin (ONB-Dox) and a multivalent FA-conjugated polyamidoamine (PAMAM) dendrimer G5(FA)6 to prepare UCN@(ONB-Dox)(G5FA). Surface plasmon resonance experiments performed with G5(FA)6 dendrimer alone show nanomolar binding avidity (KD = 5.9 × 10(-9) M) to the folate binding protein. This dendrimer binding corresponds with selective binding and uptake of UCN@(ONB-Dox)(G5FA) by FAR-positive KB carcinoma cells in vitro. Furthermore, UCN@(ONB-Dox)(G5FA) treatment of FAR(+) KB cells inhibits cell growth in a light dependent manner. These results validate the utility of modularly integrated UCN-dendrimer nanocomposites for cell type specific NIR imaging and light-controlled drug release, thus serving as a new theranostic system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Designing Tripodal and Triangular Gadolinium Oxide Nanoplates and Self-Assembled Nanofibrils as Potential Multimodal Bioimaging Probes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paik, T; Gordon, TR; Prantner, AM

2013-03-01

Here, we report the shape-controlled synthesis of tripodal and triangular gadolinium oxide (Gd2O3) nanoplates. In the presence of lithium ions, the shape of the nanocrystals is readily controlled by tailoring reaction parameters such as temperature and time. We observe that the morphology transforms from an initial tripodal shape to a triangular shape with increasing reaction time or elevated temperatures. Highly uniform Gd2O3 nanoplates are self-assembled into nanofibril-like liquid-crystalline superlattices with long-range orientational and positional order. In addition, shape-directed self-assemblies are investigated by tailoring the aspect ratio of the arms of the Gd2O3 nanoplates. Due to a strong paramagnetic response, Gd2O3more » nanocrystals are excellent candidates for MRI contrast agents and also can be doped with rare-earth ions to form nanophosphors, pointing to their potential in multimodal imaging. In this work, we investigate the MR relaxometry at high magnetic fields (9,4 and 14.1 T) and the optical properties including near-IR to visible upconversion luminescence and X-ray excited optical luminescence of doped Gd2O3 nanoplates. The complex shape of Gd2O3 nanoplates, coupled with their magnetic properties and their ability to phosphoresce under NIR or X-ray excitation which penetrate deep into tissue, makes these nanoplates a promising platform for multimodal imaging in biomedical applications.« less

Influence of Binders and Solvents on Stability of Ru/RuOx Nanoparticles on ITO Nanocrystals as Li-O2 Battery Cathodes.

PubMed

Vankova, Svetoslava; Francia, Carlotta; Amici, Julia; Zeng, Juqin; Bodoardo, Silvia; Penazzi, Nerino; Collins, Gillian; Geaney, Hugh; O'Dwyer, Colm

2017-02-08

Fundamental research on Li-O 2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li-O 2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1-2 nm oxygen evolution reaction (OER) catalyst Ru/RuO x nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li-O 2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuO x nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (<3.5 V) instead of polyvinylidene fluoride (PVDF). The Ru/RuO x /ITO nanocrystalline materials in DMSO provide efficient Li 2 O 2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuO x NPs remain effective OER catalysts for Li 2 O 2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO-EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuO x /ITO materials in Li-O 2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5-0.8 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photon up-conversion increases biomass yield in Chlorella vulgaris.

PubMed

Menon, Kavya R; Jose, Steffi; Suraishkumar, Gadi K

2014-12-01

Photon up-conversion, a process whereby lower energy radiations are converted to higher energy levels via the use of appropriate phosphor systems, was employed as a novel strategy for improving microalgal growth and lipid productivity. Photon up-conversion enables the utilization of regions of the solar spectrum, beyond the typical photosynthetically active radiation, that are usually wasted or are damaging to the algae. The effects of up-conversion of red light by two distinct sets of up-conversion phosphors were studied in the model microalgae Chlorella vulgaris. Up-conversion by set 1 phosphors led to a 2.85 fold increase in biomass concentration and a 3.2 fold increase in specific growth rate of the microalgae. While up-conversion by set 2 phosphors resulted in a 30% increase in biomass and 12% increase in specific intracellular neutral lipid, while the specific growth rates were comparable to that of the control. Furthermore, up-conversion resulted in higher levels of specific intracellular reactive oxygen species in C. vulgaris. Up-conversion of red light (654 nm) was shown to improve biomass yields in C. vulgaris. In principle, up-conversion can be used to increase the utilization range of the electromagnetic spectrum for improved cultivation of photosynthetic systems such as plants, algae, and microalgae. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared upconversion for astronomy

NASA Technical Reports Server (NTRS)

Boyd, R. W.

1977-01-01

The basic theory of upconversion is presented, along with a brief historical summary of upconversion techniques. Upconverters were used in astronomical studies, but have met with only modest success. Upconversion will become a useful detection method for astronomy only if substantial but perhaps forseeable, improvements can be realized.

Luminescence upconversion under hydrostatic pressure in the 3d-metal systems Ti2+:NaCl and Ni2+:CsCdCl3

NASA Astrophysics Data System (ADS)

Wenger, Oliver S.; Salley, G. Mackay; Valiente, Rafael; Güdel, Hans U.

2002-06-01

We present a study of upconversion materials and processes under external hydrostatic pressure. The near-infrared to visible photon upconversion properties of Ti2+-doped NaCl and Ni2+-doped CsCdCl3 at 15 K are studied as a function of external hydrostatic pressure. It is found that in Ti2+:NaCl pressure can be used to switch on an efficient upconversion mechanism, which is inactive at ambient pressure, leading to an order-of-magnitude enhancement of the overall upconversion efficiency of this material. For Ni2+:CsCdCl3 it is demonstrated that upconversion luminescence excitation spectroscopy can be used to study the pressure dependence of excited state absorption transitions. The results demonstrate the ability to tune upconversion properties by altering the local crystal field of active ions, in addition to probing the pressure dependence of excited state absorption transitions via upconversion spectroscopy.

Current Advances in Lanthanide‐Doped Upconversion Nanostructures for Detection and Bioapplication

PubMed Central

Chen, Cailing

2016-01-01

Along with the development of science and technology, lanthanide‐doped upconversion nanostructures as a new type of materials have taken their place in the field of nanomaterials. Upconversion luminescence is a nonlinear optical phenomenon, which absorbs two or more photons and emits one photon. Compared with traditional luminescence materials, upconversion nanostructures have many advantages, such as weak background interference, long lifetime, low excitation energy, and strong tissue penetration. These interesting nanostructures can be applied in anticounterfeit, solar cell, detection, bioimaging, therapy, and so on. This review is focused on the current advances in lanthanide‐doped upconversion nanostructures, covering not only basic luminescence mechanism, synthesis, and modification methods but also the design and fabrication of upconversion nanostructures, like core–shell nanoparticles or nanocomposites. At last, this review emphasizes the application of upconversion nanostructure in detection and bioimaging and therapy. Learning more about the advances of upconversion nanostructures can help us better exploit their excellent performance and use them in practice. PMID:27840794

Near-Infrared to Visible Organic Upconversion Devices Based on Organic Light-Emitting Field Effect Transistors.

PubMed

Li, Dongwei; Hu, Yongsheng; Zhang, Nan; Lv, Ying; Lin, Jie; Guo, Xiaoyang; Fan, Yi; Luo, Jinsong; Liu, Xingyuan

2017-10-18

The near-infrared (NIR) to visible upconversion devices have attracted great attention because of their potential applications in the fields of night vision, medical imaging, and military security. Herein, a novel all-organic upconversion device architecture has been first proposed and developed by incorporating a NIR absorption layer between the carrier transport layer and the emission layer in heterostructured organic light-emitting field effect transistors (OLEFETs). The as-prepared devices show a typical photon-to-photon upconversion efficiency as high as 7% (maximum of 28.7% under low incident NIR power intensity) and millisecond-scale response time, which are the highest upconversion efficiency and one of the fastest response time among organic upconversion devices as referred to the previous reports up to now. The high upconversion performance mainly originates from the gain mechanism of field-effect transistor structures and the unique advantage of OLEFETs to balance between the photodetection and light emission. Meanwhile, the strategy of OLEFETs also offers the advantage of high integration so that no extra OLED is needed in the organic upconversion devices. The results would pave way for low-cost, flexible and portable organic upconversion devices with high efficiency and simplified processing.

Optoperforation of Intact Plant Cells, Spectral Characterization of Alloy Disorder in InAsP Alloys, and Bimetallic Concentric Surfaces for Metal-Enhanced Fluorescence in Upconverting Nanocrystals

NASA Astrophysics Data System (ADS)

Merritt, Travis R.

The techniques of optoperforation, spectral characterization of alloy disorder, and metal-enhanced uorescence were applied to previously unconsidered or disregarded systems in order to demonstrate that such applications are both feasible and consequential. These applications were the subject of three disparate works and, as such, are independently discussed. Despite being ostensibly restricted to mammalian cells, optoperforation was demonstrated in intact plant cells by means of successful femtosecond-laser-mediated infiltration of a membrane impermeable dextran-conjugated dye into cells of vital Arabidopsis seedling stems. By monitoring the rate of dye uptake, and the reaction of both CFP-expressing vacuoles and nanocellulose substrates, the intensity and exposure time of the perforating laser were adjusted to values that both preserved cell vitality and permitted the laser-assisted uptake of the uorophore. By using these calibrated laser parameters, dye was injected and later observed in targeted cells after 72 hours, all without deleteriously affecting the vital functions of those cells. In the context of alloy disorder, photoluminescence of excitonic transitions in two InAsxP1--x alloys were studied through temperature and magnetic field strength dependencies, as well as compositionally-dependent time-resolved behavior. The spectral shape, behavior of the linewidths at high magnetic fields, and the divergence of the peak positions from band gap behavior at low temperatures indicated that alloy disorder exists in the x=0.40 composition while showing no considerable presence in the x=0.13 composition. The time-resolved photoluminescence spectrum for both compositions feature a fast and slow decay, with the slow decay lifetime in x=0.40 being longer than that of x=0.13, which may be due to carrier migration between localized exciton states in x=0.40. In order to achieve broadband metal-enhanced uorescence in upconverting NaYF4:Yb,Er nanocrystals, two nanocomposite architectures were proposed that retrofit metallic nanoshells to these lanthanide-doped nanocrystals. The typical monometallic construction was rejected in favor of architectures featuring Au-Ag bimetallic concentric surfaces, a decision supported by the considerable overlap of the calculated plasmon modes of the metallic structures with the emission and absorption spectrum of the nanocrystals. Furthermore, precursors of these nanocomposites were synthesized and photoluminescence measurements were carried out, ultimately verifying that these precursors produce the requisite upconversion emissions.

Color Tunable and Upconversion Luminescence in Yb-Tm Co-Doped Yttrium Phosphate Inverse Opal Photonic Crystals.

PubMed

Wang, Siqin; Qiu, Jianbei; Wang, Qi; Zhou, Dacheng; Yang, Zhengwen

2016-04-01

For this paper, YPO4: Tm, Yb inverse opals with the photonic band gaps at 475 nm and 655 nm were prepared by polystyrene colloidal crystal templates. We investigated the influence of photonic band gaps on the Tm-Yb upconversion emission which was in the YPO4: Tm Yb inverse opal photonic crystals. Comparing with the reference sample, significant suppression of both the blue and red upconversion luminescence of Tm3+ ions were observed in the inverse opals. The color purity of the blue emission was improved in the inverse opal by the suppression of red upconversion emission. Additionally, mechanism of upconversion emission in the inverse opal was discussed. We believe that the present work will be valuable for not only the foundational study of upconversion emission modification but also the development of new optical devices in upconversion lighting and display.

Dye-Sensitized Core/Active Shell Upconversion Nanoparticles for Optogenetics and Bioimaging Applications

DOE PAGES

Wu, Xiang; Zhang, Yuanwei; Takle, Kendra; ...

2016-01-06

A near-infrared (NIR) dye-sensitized upconversion nanoparticles (UCNPs) can broaden the absorption range and boost upconversion efficiency of UCNPs. We achieved significantly enhanced upconversion luminescence in dye-sensitized core/active shell UCNPs via the doping of ytterbium ions (Yb 3+ ) in the UCNP shell, which bridged the energy transfer from the dye to the UCNP core. As a result, we synergized the two most practical upconversion booster effectors (dye-sensitizing and core/shell enhancement) to amplify upconversion efficiency. We also demonstrated two biomedical applications using these UCNPs. By using dye-sensitized core/active shell UCNP embedded poly(methyl methacrylate) polymer implantable systems, we successfully shifted the optogeneticmore » neuron excitation window to a biocompatible and deep tissue penetrable 800 nm wavelength. Furthermore, UCNPs were water-solubilized with Pluronic F127 with high upconversion efficiency and can be imaged in a mouse model.« less

Experimental demonstration of plasmon enhanced energy transfer rate in NaYF4:Yb3+,Er3+ upconversion nanoparticles

PubMed Central

Lu, Dawei; Mao, Chenchen; Cho, Suehyun K.; Ahn, Sungmo; Park, Wounjhang

2016-01-01

Energy transfer upconversion (ETU) is known to be the most efficient frequency upconversion mechanism. Surface plasmon can further enhance the upconversion process, opening doors to many applications. However, ETU is a complex process involving competing transitions between multiple energy levels and it has been difficult to precisely determine the enhancement mechanisms. In this paper, we report a systematic study on the dynamics of the ETU process in NaYF4:Yb3+,Er3+ nanoparticles deposited on plasmonic nanograting structure. From the transient near-infrared photoluminescence under various excitation power densities, we observed faster energy transfer rates under stronger excitation conditions until it reached saturation where the highest internal upconversion efficiency was achieved. The experimental data were analyzed using the complete set of rate equations. The internal upconversion efficiency was found to be 56% and 36%, respectively, with and without the plasmonic nanograting. We also analyzed the transient green emission and found that it is determined by the infrared transition rate. To our knowledge, this is the first report of experimentally measured internal upconversion efficiency in plasmon enhanced upconversion material. Our work decouples the internal upconversion efficiency from the overall upconverted luminescence efficiency, allowing more targeted engineering for efficiency improvement. PMID:26739230

Multiphoton microscopy and image guided light activated therapy using nanomaterials (Conference Presentation)

NASA Astrophysics Data System (ADS)

Prasad, Paras N.

2017-02-01

This talk will focus on design and applications of nanomaterials exhibiting strong multiphoton upconversion for multiphoton microscopy as well as for image-guided and light activated therapy .1-3 Such processes can occur by truly nonlinear optical interactions proceeding through virtual intermediate states or by stepwise coupled linear excitations through real intermediate states. Multiphoton processes in biocompatible multifunctional nanoparticles allow for 3D deep tissue imaging. In addition, they can produce in-situ photon conversion of deep tissue penetrating near IR light into a needed shorter wavelength light for photo-activated therapy at a targeted site, thus overcoming the limited penetration of UV or visible light into biological media. We are using near IR emitters such as silicon quantum dots which also exhibit strong multiphoton excitation for multiphoton microscopy. Another approach involves nonlinear nanocrystals such as ZnO which can produce four wave mixing, sum frequency generation as well as second harmonic generation to convert a deep tissue penetrating Near IR light at the targeted biological site to a desired shorter wavelength light suitable for bio imaging or activation of a therapy. We have utilized this approach to activate a photosensitizer for photodynamic therapy. Yet another type of upconversion materials is rare-earth ion doped optical nanotransformers which transform a Near IR (NIR) light from an external source by sequential single photon absorption, in situ and on demand, to a needed wavelength. Applications of these nanotransformers in multiphoton photoacoustic imaging will also be presented. An exciting direction pursued by us using these multiphoton nanoparticles, is functional imaging of brain. Simultaneously, they can effect optogenetics for regioselective stimulation of neurons for providing an effective intervention/augmentation strategy to enhance the cognitive state and lead to a foundation for futuristic vision of super human capabilities. Challenges and opportunities will be discussed.

New Triplet Sensitization Routes for Photon Upconversion: Thermally Activated Delayed Fluorescence Molecules, Inorganic Nanocrystals, and Singlet-to-Triplet Absorption.

PubMed

Yanai, Nobuhiro; Kimizuka, Nobuo

2017-10-17

Photon upconversion based on triplet-triplet annihilation (TTA-UC) has attracted much interest because of its possible applications to renewable energy production and biological fields. In particular, the UC of near-infrared (NIR) light to visible (vis) light is imperative to overcome the Shockley-Queisser limit of single-junction photovoltaic cells, and the efficiency of photocatalytic hydrogen production from water can also be improved with the aid of vis-to-ultraviolet (UV) UC. However, both processes have met limitations in the wavelength range, efficiency, and sensitivity for weak incident light. This Account describes recent breakthroughs that solve these major problems, new triplet sensitization routes to significantly enlarge the range of conversion wavelength by minimizing the energy loss during intersystem crossing (ISC) of triplet sensitizers or bypassing the ISC process. The photochemical processes of TTA-UC in general start with the absorption of longer wavelength incident light by triplet sensitizers, which generate the triplet states via ISC. This ISC inevitably accompanies the energy loss of hundreds of millielectronvolts, which significantly limits the TTA-UC with large anti-Stokes shifts. The small S 1 -T 1 gap of molecules showing thermally activated delayed fluorescence (TADF) allows the sensitization of emitters with the highest T 1 and S 1 energy levels ever employed in TTA-UC, which results in efficient vis-to-UV UC. As alternatives to molecular sensitizers in the NIR region, inorganic nanocrystals with broad NIR absorption bands have recently been shown to work as effective sensitizers for NIR-to-vis TTA-UC. Their small exchange splitting minimizes the energy loss during triplet sensitization. The modification of nanocrystal surfaces with organic acceptors via coordination bonds allows efficient energy transfer between the components and succeeding TTA processes. To remove restrictions on the energy loss during ISC, molecules with direct singlet-to-triplet (S-T) excitation are employed as triplet sensitizers. Although the S-T absorption is spin forbidden, large spin-orbital coupling occurs for appropriately designed metal complexes, which allow S-T absorption in the NIR region with large absorption coefficients. While the triplet lifetime of such S-T absorption sensitizers is often short (less than microsecond), the integration of the molecular sensitizers with emitter assemblies allows facile Dexter energy transfer to the surrounding emitter molecules, leading to efficient NIR-to-vis UC emission through triplet energy migration (TEM) in the condensed state. By judicious modification of the chromophore structures, the first example of NIR-to-blue UC has also been achieved. It is essential to combine these new triplet sensitization routes with an upconverted energy collection (UPCON) approach in molecular assemblies to effectively populate emitter triplets and to overcome remaining issues including back energy transfer. We propose two overall materials designs for the TEM-UPCON strategy, core-shell-shell structures and trilayer structures composed of triplet donor, acceptor, and energy collector. The fusion between triplet science and chemistry of self-assembly would overcome previous difficulties of NIR-to-vis and vis-to-UV TTA-UC toward real-world applications ranging from energy to biology.

Up-conversion fluorescence: noncoherent excitation by sunlight.

PubMed

Baluschev, S; Miteva, T; Yakutkin, V; Nelles, G; Yasuda, A; Wegner, G

2006-10-06

We demonstrate up-conversion of noncoherent sunlight realized by ultralow excitation intensity. The bimolecular up-conversion process in our systems relies on the presence of a metastable triplet excited state, and thus has dramatically different photophysical characteristics relative to the other known methods for photon up-conversion (two-photon absorption, parametric processes, second harmonic generation, sequential multiphoton absorption, etc.).

Spectral evidence for multi-pathway contribution to the upconversion pathway in NaYF4:Yb3+,Er3+ phosphors.

PubMed

Cho, Youngho; Song, Si Won; Lim, Soo Yeong; Kim, Jae Hun; Park, Chan Ryang; Kim, Hyung Min

2017-03-08

Although upconversion phosphors have been widely used in nanomedicine, laser engineering, bioimaging, and solar cell technology, the upconversion luminescence mechanism of the phosphors has been fiercely debated. A comprehensive understanding of upconversion photophysics has been significantly impeded because the number of photons incorporated in the process in different competitive pathways could not be resolved. Few convincing results to estimate the contribution of each of the two-, three-, and four-photon channels of near-infrared (NIR) energy have been reported in yielding upconverted visible luminescence. In this study, we present the energy upconversion process occurring in NaYF 4 :Yb 3+ ,Er 3+ phosphors as a function of excitation frequency and power density. We investigated the upconversion mechanism of lanthanide phosphors by comparing UV/VIS one-photon excitation spectra and NIR multi-photon spectra. A detailed analysis of minor transitions in one-photon spectra and luminescence decay enables us to assign electronic origins of individual bands in multi-photon upconversion luminescence and provides characteristic transitions representing the corresponding upconversion channel. Furthermore, we estimated the quantitative contribution of multiple channels with respect to irradiation power and excitation energy.

Photoluminescence upconversion at GaAs /InGa P2 interfaces driven by a sequential two-photon absorption mechanism

NASA Astrophysics Data System (ADS)

Hylton, N. P.; Hinrichsen, T. F.; Vaquero-Stainer, A. R.; Yoshida, M.; Pusch, A.; Hopkinson, M.; Hess, O.; Phillips, C. C.; Ekins-Daukes, N. J.

2016-06-01

This paper reports on the results of an investigation into the nature of photoluminescence upconversion at GaAs /InGa P2 interfaces. Using a dual-beam excitation experiment, we demonstrate that the upconversion in our sample proceeds via a sequential two-photon optical absorption mechanism. Measurements of photoluminescence and upconversion photoluminescence revealed evidence of the spatial localization of carriers in the InGa P2 material, arising from partial ordering of the InGa P2 . We also observed the excitation of a two-dimensional electron gas at the GaAs /InGa P2 heterojunction that manifests as a high-energy shoulder in the GaAs photoluminescence spectrum. Furthermore, the results of upconversion photoluminescence excitation spectroscopy demonstrate that the photon energy onset of upconversion luminescence coincides with the energy of the two-dimensional electron gas at the GaAs /InGa P2 interface, suggesting that charge accumulation at the interface can play a crucial role in the upconversion process.

Ultrasmall, water dispersible, TWEEN80 modified Yb:Er:NaGd(WO4)2 nanoparticles with record upconversion ratiometric thermal sensitivity and their internalization by mesenchymal stem cells

NASA Astrophysics Data System (ADS)

Cascales, Concepción; Paíno, Carlos L.; Bazán, Eulalia; Zaldo, Carlos

2017-05-01

This work presents the synthesis by coprecipitation of diamond shaped Yb:Er:NaGd(WO4)2 crystalline nanoparticles (NPs) with diagonal dimensions in the 5-7 nm × 10-12 nm range which have been modified with TWEEN80 for their dispersion in water, and their interaction with mesenchymal stem cells (MSCs) proposed as cellular NP vehicles. These NPs belong to a large family of tetragonal Yb:Er:NaT(XO4)2 (T = Y, La, Gd, Lu; X = Mo, W) compounds with green (2H11/2 + 4S3/2 → 4I15/2) Er-related upconversion (UC) efficiency comparable to that of Yb:Er:β-NaYF4 reference compound, but with a ratiometric thermal sensitivity (S) 2.5-3.5 times larger than that of the fluoride. At the temperature range of interest for biomedical applications (˜293-317 K/20-44 °C) S = 108-118 × 10-4 K-1 for 20 at%Yb:5 at%Er:NaGd(WO4)2 NPs, being the largest values so far reported using the 2H11/2/4S3/2 Er intensity ratiometric method. Cultured MSCs, incubated with these water NP emulsions, internalize and accumulate the NPs enclosed in endosomes/lysosomes. Incubations with up to 10 μg of NPs per ml of culture medium maintain cellular metabolism at 72 h. A thermal assisted excitation path is discussed as responsible for the UC behavior of Yb:Er:NaT(XO4)2 compounds.

Er{sup 3+}/Yb{sup 3+}co-doped bismuth molybdate nanosheets upconversion photocatalyst with enhanced photocatalytic activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adhikari, Rajesh; Gyawali, Gobinda; Cho, Sung Hun

2014-01-15

In this paper, we report the microwave hydrothermal synthesis of Er{sup 3+}/Yb{sup 3+} co-doped Bi{sub 2}MoO{sub 6} upconversion photocatalyst. Crystal structure, morphology, elemental composition, optical properties and BET surface area were analyzed in detail. Infrared to visible upconversion luminescence at 532 nm and 546 nm of the co-doped samples was investigated under excitation at 980 nm. The results revealed that the co-doping of Er{sup 3+}/Yb{sup 3+} into Bi{sub 2}MoO{sub 6} exhibited enhanced photocatalytic activity for the decomposition of rhodamine B under simulated solar light irradiation. Enhanced photocatalytic activity can be attributed to the energy transfer between Er{sup 3+}/Yb{sup 3+} andmore » Bi{sub 2}MoO{sub 6} via infrared to visible upconversion from Er{sup 3+}/Yb{sup 3+} ion and higher surface area of the Bi{sub 2}MoO{sub 6} nanosheets. Therefore, this synthetic approach may exhibit a better alternative to fabricate upconversion photocatalyst for integral solar light absorption. - Graphical abstract: Schematic illustration of the upconversion photocatalysis. Display Omitted - Highlights: • Er{sup 3+}/Yb{sup 3+} co-doped Bi{sub 2}MoO{sub 6} upconversion photocatalyst is successfully synthesized. • We obtained the nanosheets having high surface area. • Upconversion of IR to visible light was confirmed. • Upconversion phenomena can be utilized for effective photocatalysis.« less

Upconversion excitations in Pr3+-doped BaY2F8 crystal

NASA Astrophysics Data System (ADS)

Piramidowicz, R.; Mahiou, R.; Boutinaud, P.; Malinowski, M.

2011-09-01

We report the orange-to-blue and infrared-(IR)-to-blue wavelengths upconversion luminescence in Pr3+:BaY2F8 crystals. Mechanism of the orange light upconversion into blue 3P0 state emission was confirmed to be energy transfer between two Pr3+ ions in the 1D2 state. IR-to-blue upconversion has only been observed under two different color IR pumping. The first resonant step was the 3H4→1G4 ground state absorption transition, and the second resonant transition was the excited state absorption from the 1G4 to 1I6 and 3PJ levels. A comparison of the efficiency of the IR-to-blue upconversion in several praseodymium activated host is presented and discussed. A model of the IR pumped upconversion praseodymium blue laser is presented and the population inversion conditions are calculated.

An Nd3+-sensitized upconversion nanophosphor modified with a cyanine dye for the ratiometric upconversion luminescence bioimaging of hypochlorite

NASA Astrophysics Data System (ADS)

Zou, Xianmei; Liu, Yi; Zhu, Xingjun; Chen, Min; Yao, Liming; Feng, Wei; Li, Fuyou

2015-02-01

Excessive or misplaced production of ClO- in living systems is usually associated with many human diseases. Therefore, it is of great importance to develop an effective and sensitive method to detect ClO- in living systems. Herein, we designed an 808 nm excited upconversion luminescence nanosystem, composed of the Nd3+-sensitized core-shell upconversion nanophosphor NaYF4:30%Yb,1%Nd,0.5%Er@NaYF4:20%Nd, which serves as an energy donor, and the ClO--responsive cyanine dye hCy3, which acts as an energy acceptor, for ratiometric upconversion luminescence (UCL) monitoring of ClO-. The detection limit of ClO- for this nanoprobe in aqueous solution is 27 ppb and the nanoprobe was successfully used to detect the ClO- in the living cells by ratiometric upconversion luminescence. Importantly, the nanoprobe realized the detection of ClO- in a mouse model of arthritis, which produced an excess of ROS, under 808 nm irradiation in vivo. The excitation laser efficiently reduced the heating effect, compared to the commonly used 980 nm laser for upconversion systems.Excessive or misplaced production of ClO- in living systems is usually associated with many human diseases. Therefore, it is of great importance to develop an effective and sensitive method to detect ClO- in living systems. Herein, we designed an 808 nm excited upconversion luminescence nanosystem, composed of the Nd3+-sensitized core-shell upconversion nanophosphor NaYF4:30%Yb,1%Nd,0.5%Er@NaYF4:20%Nd, which serves as an energy donor, and the ClO--responsive cyanine dye hCy3, which acts as an energy acceptor, for ratiometric upconversion luminescence (UCL) monitoring of ClO-. The detection limit of ClO- for this nanoprobe in aqueous solution is 27 ppb and the nanoprobe was successfully used to detect the ClO- in the living cells by ratiometric upconversion luminescence. Importantly, the nanoprobe realized the detection of ClO- in a mouse model of arthritis, which produced an excess of ROS, under 808 nm irradiation in vivo. The excitation laser efficiently reduced the heating effect, compared to the commonly used 980 nm laser for upconversion systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06407k

Near-infrared photocatalysts of BiVO4/CaF2:Er3+, Tm3+, Yb3+ with enhanced upconversion properties

NASA Astrophysics Data System (ADS)

Huang, Shouqiang; Zhu, Nanwen; Lou, Ziyang; Gu, Lin; Miao, Chen; Yuan, Haiping; Shan, Aidang

2014-01-01

Upconversion photocatalysts have the potential to absorb the near-infrared (NIR) light in solar energy and improve the photocatalytic performance. A hierarchical upconversion photocatalyst of BiVO4 (BVO)/CaF2:Er3+, Tm3+, Yb3+ (CF) combined with the narrow-band semiconductor of BVO and the luminescence agent of CF to enhance upconversion properties was synthesized via the hydrothermal method. The CF particles were deposited homogeneously on the surface of the BVO/CF composite with regular dendritic structure, which led to efficient upconversion emissions. The upconversion emission intensity of the BVO/CF composite was 8 times higher than that of pure CF, through tailoring the crystal symmetry of lanthanide ions by Bi3+ ions. The upconverted ultraviolet (361 and 379 nm), violet (408 nm), and blue (485 nm) light was able to excite BVO for photocatalysis in BVO/CF under NIR irradiation, which improved the degradation rate of methyl orange (MO).Upconversion photocatalysts have the potential to absorb the near-infrared (NIR) light in solar energy and improve the photocatalytic performance. A hierarchical upconversion photocatalyst of BiVO4 (BVO)/CaF2:Er3+, Tm3+, Yb3+ (CF) combined with the narrow-band semiconductor of BVO and the luminescence agent of CF to enhance upconversion properties was synthesized via the hydrothermal method. The CF particles were deposited homogeneously on the surface of the BVO/CF composite with regular dendritic structure, which led to efficient upconversion emissions. The upconversion emission intensity of the BVO/CF composite was 8 times higher than that of pure CF, through tailoring the crystal symmetry of lanthanide ions by Bi3+ ions. The upconverted ultraviolet (361 and 379 nm), violet (408 nm), and blue (485 nm) light was able to excite BVO for photocatalysis in BVO/CF under NIR irradiation, which improved the degradation rate of methyl orange (MO). Electronic supplementary information (ESI) available: Additional tables and figures. See DOI: 10.1039/c3nr05266d

Infrared Signal Detection by Upconversion Technique

NASA Technical Reports Server (NTRS)

Wong, Teh-Hwa; Yu, Jirong; Bai, Yingxin; Johnson, William E.

2014-01-01

We demonstrated up-conversion assisted detection of a 2.05-micron signal by using a bulk periodically poled Lithium niobate crystal. The 94% intrinsic up-conversion efficiency and 22.58% overall detection efficiency at pW level of 2.05-micron was achieved.

Spatial height directed microfluidic synthesis of transparent inorganic upconversion nano film

NASA Astrophysics Data System (ADS)

Liu, Xiaoxia; Zhu, Cheng; Liao, Wei; Jin, Junyang; Ni, Yaru; Lu, Chunhua; Xu, Zhongzi

2017-11-01

A microfluidic-based synthesis of an inorganic upconversion nano film has been developed with a large area of dense-distributed NaYF4 crystal grains in a silica glass micro-reactor and the film exhibits high transparence, strong upconversion luminescence and robust adhesion with the substrate. The spatial heights of micro-reactors are tuned between 31 and 227 mm, which can regulate flow regimes. The synergistic effect of spatial height and fluid regime is put forward, which influences diffusion paths and assembly ways of different precursor molecules and consequently directs final distributions and morphologies of crystal grains, as well as optical properties due to diversity of surface and thickness of films. The spatial height of 110 mm is advantageous for high transmittance of upconversion film due to the flat surface and appropriate film thickness of 67 nm. The height of 150 mm is in favor of uniform distribution of upconversion fluorescence and achieving the strongest fluorescence due to minimized optical loss. Such a transparent upconversion film with a large area of uniform distribution is promising to promote the application of upconversion materials and spatial height directed microfluidic regime have a certain significance on many microfluidic synthesis.

The Quality of In Vivo Upconversion Fluorescence Signals Inside Different Anatomic Structures.

PubMed

Wang, Lijiang; Draz, Mohamed Shehata; Wang, Wei; Liao, Guodong; Xu, Yuhong

2015-02-01

Fluorescence imaging is a broadly interesting and rapidly growing strategy for non-invasive clinical applications. However, because of interference from light scattering, absorbance, and tissue autofluorescence, the images can exhibit low sensitivity and poor quality. Upconversion fluorescence imaging, which is based on the use of near-infrared (NIR) light for excitation, has recently been introduced as an improved approach to minimize the effects of light scattering and tissue autofluorescence. This strategy is promising for ultrasensitive and deep tissue imaging applications. However, the emitted upconversion fluorescence signals are primarily in the visible range and are likely to be absorbed and scattered by tissues. Therefore, different anatomic structures could impose various effects on the quality of the images. In this study, we used upconversion-core/silica-shell nanoprobes to evaluate the quality of upconversion fluorescence at different anatomic locations in athymic nude mice. The nanoprobe contained an upconversion core, which was green (β-NaYF4:Yb3+/Ho3+) or red (β-NaYF4:Yb3+/Er3+), and a nonporous silica shell to allow for multicolor imaging. High-quality upconversion fluorescence signals were detected with signal-to-noise ratios of up to 170 at tissue depths of up to - 1.0 cm when a 980 nm laser excitation source and a bandpass emission filter were used. The presence of dense tissue structures along the imaging path reduced the signal intensity and imaging quality, and nanoprobes with longer-wavelength emission spectra were therefore preferable. This study offers a detailed analysis of the quality of upconversion signals in vivo inside different anatomic structures. Such information could be essential for the analysis of upconversion fluorescence images in any in vivo biodiagnostic and microbial tracking applications.

The structure of Er3+-doped oxy-fluoride transparent glass-ceramics studied by Raman scattering

NASA Astrophysics Data System (ADS)

Tikhomirov, V. K.; Seddon, A. B.; Ferrari, M.; Montagna, M.; Santos, L. F.; Almeida, R. M.

2003-11-01

We show that the structure of transparent oxy-fluoride glass-ceramics formed by heat treatment of glasses of typical composition 32(SiO2):9(AlO1.5):31.5(CdF2):18.5(PbF2): 5.5(ZnF2):3.5(ErF3) mol% consists of ~ 12 nm diameter, Er3+-doped, β-PbF2 nano-crystals embedded in a silica-based glass network and connected to it via non-bridging O and F anions, or fluorine linkages such as Pb-F-Cd and Pb-F-Zn. It is proposed that the glass network structure is mostly chain-like and dominated by Si(O,F)4 tetrahedra with two bridging O and two non-bridging O and/or F atoms (Q2 units). SiO4 tetrahedra with zero and one bridging O (Q0 and Q1 units, respectively) are also present in the glass structure, in the approximate proportion Q0:Q1:Q2 = 1:1:3, a characteristic which appears to be of primary importance. The flexible, chain-like glass-network, with many broken bonds, results in easy accommodation of the Er3+-doped PbF2 nano-crystals, which are grown by heat-treatment of the precursor glass. The boson peak in the Raman spectrum of the precursor glass decreases in intensity upon ceramming and is partly converted to narrow crystalline peaks at lower frequency, consistent with the precipitation of PbF2 crystalline nano-particles. It is suggested that the boson peak involves localized vibrations of broken or stretched Pb-F bonds. The mean free path for these vibrations increases with ceramming, which involves partial crystallization of the glass network, resulting in a shift of the boson peak vibrations to lower-frequency crystalline peaks.

Improvement of Er 3+ emissions in oxyfluoride glass ceramic nano-composite by thermal treatment

NASA Astrophysics Data System (ADS)

Chen, Daqin; Wang, Yuansheng; Yu, Yunlong; Ma, En

2006-05-01

In order to improve the 1.53 μm emission of Er 3+-doped oxyfluoride glass ceramic containing CaF 2 nano-crystals, series of samples with same Er 3+ doping lever thermal treated under different conditions were prepared. The UV-VIR-NIR absorption spectra, near-infrared and up-conversion emission spectra, and 4I13/2 decay curves were measured. Based on Judd-Ofelt theory, the radiative transition probability, fluorescence branching ratio and radiative decay time of various metastable transitions of precursor glass and glass ceramics were evaluated. With the increasing of heating temperature, the Judd-Ofelt intensity parameter Ω2 monotonously decreased from 4.39×10 -20 to 2.72×10 -20 cm 2; the emission lifetime and quantum efficiency significantly increased from 5.9 to 8.0 ms and 70% to 98%, respectively. The wavelength dependence of gain cross-sections of oxyfluoride glass and glass ceramics were computed to be relatively flat in the range of 1530-1565 nm for population inversion from 0.7 to 1.0.

Up-conversion luminescence of Er3+ ions in lead-free germanate glasses under 800 nm and 980 nm cw diode laser excitation

NASA Astrophysics Data System (ADS)

Janek, J.; Lisiecki, R.; Ryba-Romanowski, W.; Pisarska, J.; Pisarski, W. A.

2017-12-01

Up-conversion luminescence spectra of Er3+ ions in multicomponent oxyfluoride glasses GeO2 - BaO - BaF2 - Ga2O3 - Er2O3 were examined. It was found that the up-conversion luminescence spectra of Er3+ are dependent on pumping wavelengths. The spectra recorded upon the excitation at 800 nm contained an intense green up-conversion luminescence corresponding to the 2H11/2,4S3/2 → 4I15/2 transitions and a very weak red luminescence related to the 4F9/2 - 4I15/2 transition. In spectra recorded upon 980 nm excitation the contribution of the red luminescence was markedly higher. The interaction mechanisms involved in up-conversion processes are proposed and observed dependence of intensity of up-converted luminescence on excitation power is discussed. The experimental results suggest that Er3+ singly doped lead-free oxyfluoride germanate glass is useful for up-conversion luminescence applications.

Photon energy upconversion through thermal radiation with the power efficiency reaching 16%.

PubMed

Wang, Junxin; Ming, Tian; Jin, Zhao; Wang, Jianfang; Sun, Ling-Dong; Yan, Chun-Hua

2014-11-28

The efficiency of many solar energy conversion technologies is limited by their poor response to low-energy solar photons. One way for overcoming this limitation is to develop materials and methods that can efficiently convert low-energy photons into high-energy ones. Here we show that thermal radiation is an attractive route for photon energy upconversion, with efficiencies higher than those of state-of-the-art energy transfer upconversion under continuous wave laser excitation. A maximal power upconversion efficiency of 16% is achieved on Yb(3+)-doped ZrO2. By examining various oxide samples doped with lanthanide or transition metal ions, we draw guidelines that materials with high melting points, low thermal conductivities and strong absorption to infrared light deliver high upconversion efficiencies. The feasibility of our upconversion approach is further demonstrated under concentrated sunlight excitation and continuous wave 976-nm laser excitation, where the upconverted white light is absorbed by Si solar cells to generate electricity and drive optical and electrical devices.

Observing quantum control of up-conversion luminescence in Dy3+ ion doped glass from weak to intermediate shaped femtosecond laser fields

NASA Astrophysics Data System (ADS)

Liu, Pei; Cheng, Wenjing; Yao, Yunhua; Xu, Cheng; Zheng, Ye; Deng, Lianzhong; Jia, Tianqing; Qiu, Jianrong; Sun, Zhenrong; Zhang, Shian

2017-11-01

Controlling the up-conversion luminescence of rare-earth ions in real-time, in a dynamical and reversible manner, is very important for their application in laser sources, fiber-optic communications, light-emitting diodes, color displays and biological systems. In previous studies, the up-conversion luminescence control mainly focused on the weak femtosecond laser field. Here, we further extend this control behavior from weak to intermediate femtosecond laser fields. In this work, we experimentally and theoretically demonstrate that the up-conversion luminescence in Dy3+ ion doped glass can be artificially controlled by a π phase step modulation, but the up-conversion luminescence control behavior will be affected by the femtosecond laser intensity, and the up-conversion luminescence is suppressed by lower laser intensity while enhanced by higher laser intensity. We establish a new theoretical model (i.e. the fourth-order perturbation theory) to explain the physical control mechanism by considering the two- and four-photon absorption processes, and the theoretical results show that the relative weight of four-photon absorption in the whole excitation process will increase with the increase in laser intensity, and the interference between two- and four-photon absorptions results in up-conversion luminescence control modulation under different laser intensities. These theoretical and experimental works can provide a new method to control and understand up-conversion luminescence in rare-earth ions, and also may open a new opportunity to the related application areas of rare-earth ions.

Interactions of DNA coated upconversion nanoparticles with 2D materials

NASA Astrophysics Data System (ADS)

Giust, Davide; Lucío, María. Isabel; Muskens, Otto L.; Kanaras, Antonios G.

2018-02-01

In this work we investigated the nature of quenching between different types of 2D materials (WS2, MoS2 and graphene oxide) and oligonucleotide coated-upconversion nanoparticles. This study contributes towards the efficient design of biosensors based on 2D materials and DNA-coated upconversion nanoparticles.

Upconversion fiber-optic confocal microscopy under near-infrared pumping.

PubMed

Kim, Do-Hyun; Kang, Jin U; Ilev, Ilko K

2008-03-01

We present a simple upconversion fiber-optic confocal microscope design using a near-infrared laser for pumping of a rare-earth-doped glass powder. The nonlinear optical frequency conversion process is highly efficient with more than 2% upconversion fluorescence efficiency at a near-infrared pumping wavelength of 1.55 microm. The upconversion confocal design allows the use of conventional Si detectors and 1.55 microm near-infrared pump light. The lateral and axial resolutions of the system were equal to or better than 1.10 and 13.11 microm, respectively.

High efficiency upconversion nanophosphors for high-contrast bioimaging

NASA Astrophysics Data System (ADS)

Alkahtani, Masfer H.; Alghannam, Fahad S.; Sanchez, Carlos; Gomes, Carmen L.; Liang, Hong; Hemmer, Philip R.

2016-12-01

Upconversion nanoparticles (UCNPs) are of interest because they allow suppression of tissue autofluorescence and are therefore visible deep inside biological tissue. Compared to upconversion dyes, UCNPs have a lower pump intensity threshold, better photostability, and less toxicity. Recently, YVO4: Er+3, Yb+3 nanoparticles were shown to exhibit strong up-conversion luminescence with a relatively low 10 kW cm-2 excitation intensity even in water, which makes them excellent bio-imaging candidates. Herein, we investigate their use as internal probes in insects by injecting YVO4 : Er+3, Yb+3 nanoparticles into fire ants as a biological model, and obtain 2D optical images with 980 nm illumination. High-contrast images with high signal-to-noise ratio are observed by detecting the up-conversion fluorescence as the excitation laser is scanned.

Laser-diode-excited blue upconversion in Tm3+/Yb3+ -codoped TeO2-Ga2O3-R2O (R=Li, Na, K) glasses.

PubMed

Zhao, Chun; Zhang, Qinyuan; Yang, Gangfeng; Jiang, Zhonghong

2008-01-01

This paper reports on intense blue upconversion in Tm(3+)/Yb(3+) codoped TeO(2)-Ga(2)O(3)-R(2)O(R=Li, Na, K) glasses upon excitation with commercial available laser diode (LD). Effects of alkali ions on the Raman spectra, thermal stability and spectroscopic properties of the tellurite-gallium glasses have also been investigated. Energy transfer and the involved upconversion mechanisms have been discussed. Intense blue upconversion emission centered at 476 nm along with a weak red emission at 650 nm has been observed upon excitation of 977 nm LD, assigned to the transitions of 1G4-->3H6, and 1G4-->3H4 and/or 3F(2,3)-->3H6 of Tm(3+), respectively. The blue upconversion intensity has a cubelike dependence on incident pump laser power, indicating a three-photon process. However, a quadratic dependence of the 476 nm upconversion intensity on the incident pump laser power has been observed when samples under excitation of 808 nm LD due to a two-photon absorption process. Enhanced upconversion luminescence have been observed with replacing K(+) for Na(+) and Li(+).

Divalent europium doped CaF 2 and BaF 2 nanocrystals from ionic liquids

DOE PAGES

Anghel, Sergiu; Golbert, Sebastian; Meijerink, Andries; ...

2016-10-11

A new, facile and quick synthesis method for Eu 2+ doped the alkaline earth fluorides was developed using ionic liquids as solvent, precursor and capping agent. Reductive atmosphere and very high temperatures were avoided, while still attaining the desired structure, small particle sizes and divalent oxidation state of the lanthanide. Here, this opens the door for the development of new Ln 2+ doped nanomaterials. Here, the successful Eu 2+ incorporation was proven by optical spectroscopic measurements which showed the spin and parity allowed f-d transitions of Eu 2+ in CaF 2:Eu 2+/BaF 2:Eu 2+. 4f 7-4f 7 transitions could bemore » observed at low temperatures (7 K).« less

Enhanced upconversion emission in colloidal (NaYF4:Er(3+))/NaYF4 core/shell nanoparticles excited at 1523 nm.

PubMed

Shao, Wei; Chen, Guanying; Damasco, Jossana; Wang, Xianliang; Kachynski, Aliaksandr; Ohulchanskyy, Tymish Y; Yang, Chunhui; Ågren, Hans; Prasad, Paras N

2014-03-15

In this work, we report on efficient visible and near-IR upconversion emissions in colloidal hexagonal-phase core/shell NaYF4:Er(3+)/NaYF4 nanoparticles (∼38  nm) under IR laser excitation at 1523 nm. Varying amounts of Er(3+) dopants were introduced into the core NaYF4:Er(3+) nanoparticles, revealing an optimized Er(3+) concentration of 10% for the highest luminescent efficiency. An inert epitaxial shell layer of NaYF4 grown onto the core of the NaYF4:Er(3+) 10% nanoparticle increased its upconversion emission intensity fivefold due to suppression of surface-related quenching mechanisms, yielding the absolute upconversion efficiency to be as high as ∼3.9±0.3% under an excitation density of 18  W/cm(2). The dependence of the intensity of upconversion emission peaks on laser excitation density in the core/shell nanoparticle displayed "saturation effects" at low excitation density in the range of 1.5-18  W/cm(2), which again demonstrates high upconversion efficiency.

Efficient upconversion emission in Ho3+/Nd3+ co-doped oxyfluorosilicate glasses

NASA Astrophysics Data System (ADS)

Devarajulu, G.; Raju, B. Deva Prasad

2018-04-01

We report on an efficient Ho3+ and Ho3+/Nd3+ co-doped oxyfluorosilicate glasses upon excitation with an 808 nm laser diode. The detailed fluorescence have been studied under this excitation source and energy transfer mechanisms in Ho3+/Nd3+ co-doped oxyfluorosilicate glasses. The upconversion peaks at 486, 547 and 596 nm were observed in Nd3+/Ho3+ co-doped sample. The intensity of upconversion emission transitions in Ho3+ depends on the neodymium codopent concentration. These results indicate that Nd3+ ions can be potentially used as sensitizer for Ho3+ ions to stimulate the intense upconversion emission. The energy transfer mechanism between Nd3+ and Ho3+ was analyzed pursuant to the absorption spectra, upconversion spectra and the energy level structures of Nd3+ and Ho3+ ions have been briefly discussed.

Low-noise mid-IR upconversion detector for improved IR-degenerate four-wave mixing gas sensing.

PubMed

Høgstedt, Lasse; Dam, Jeppe Seidelin; Sahlberg, Anna-Lena; Li, Zhongshan; Aldén, Marcus; Pedersen, Christian; Tidemand-Lichtenberg, Peter

2014-09-15

We compare a nonlinear upconversion detector with a conventional cryogenic InSb detector for the detection of coherent infrared light showing near-shot-noise-limited performance in the upconversion system. The InSb detector is limited by dark noise, which results in a 500 times lower signal-to-noise ratio. The two detectors are compared for the detection of a coherent degenerate four-wave mixing (DFWM) signal in the mid-infrared, and applied to measure trace-level acetylene in a gas flow at atmospheric pressure, probing its fundamental rovibrational transitions. In addition to lower noise, the upconversion system provides image information of the signal, thus adding new functionality compared to standard point detection methods. We further show that the upconversion detector system can be implemented as a simple replacement of the cryogenic detector.

Upconversion luminescence in BaMoO{sub 4}:Pr{sup 3+} phosphor for display devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soni, Abhishek Kumar; Rai, Vineet Kumar, E-mail: vineetkrrai@yahoo.co.in

2015-08-28

The frequency upconversion is an important nonlinear optical property by which near infrared light is converted into the visible light. The BaMoO{sub 4}:Pr{sup 3+} powder phosphor has been synthesized by solid state reaction method. The upconversion emission bands are recorded under the excitation of 808 nm diode laser. The phase formation of the prepared phosphor has been identified by powder X-ray diffraction (XRD) technique. The upconversion emission mechanism and colour coordinate have been explained by using energy level and CIE (International Commission on Illumination) chromaticity diagram study, respectively.

Magnetoelectricity in CoFe2O4 nanocrystal-P(VDF-HFP) thin films

PubMed Central

2013-01-01

Transition metal ferrites such as CoFe2O4, possessing a large magnetostriction coefficient and high Curie temperature (Tc > 600 K), are excellent candidates for creating magnetic order at the nanoscale and provide a pathway to the fabrication of uniform particle-matrix films with optimized potential for magnetoelectric coupling. Here, a series of 0–3 type nanocomposite thin films composed of ferrimagnetic cobalt ferrite nanocrystals (8 to 18 nm) and a ferroelectric/piezoelectric polymer poly(vinylidene fluoride-co-hexafluoropropene), P(VDF-HFP), were prepared by multiple spin coating and cast coating over a thickness range of 200 nm to 1.6 μm. We describe the synthesis and structural characterization of the nanocrystals and composite films by XRD, TEM, HRTEM, STEM, and SEM, as well as dielectric and magnetic properties, in order to identify evidence of cooperative interactions between the two phases. The CoFe2O4 polymer nanocomposite thin films exhibit composition-dependent effective permittivity, loss tangent, and specific saturation magnetization (Ms). An enhancement of the effective permittivity and saturation magnetization of the CoFe2O4-P(VDF-HFP) films was observed and directly compared with CoFe2O4-polyvinylpyrrolidone, a non-ferroelectric polymer-based nanocomposite prepared by the same method. The comparison provided evidence for the observation of a magnetoelectric effect in the case of CoFe2O4-P(VDF-HFP), attributed to a magnetostrictive/piezoelectric interaction. An enhancement of Ms up to +20.7% was observed at room temperature in the case of the 10 wt.% CoFe2O4-P(VDF-HFP) sample. PMID:24004499

Upconversion luminescent logic gates and turn-on sensing of glutathione based on two-photon excited quantum dots conjugated with dopamine.

PubMed

Gui, Rijun; Jin, Hui; Liu, Xifeng; Wang, Zonghua; Zhang, Feifei; Xia, Jianfei; Yang, Min; Bi, Sai

2014-12-07

Under the two-photon excitation, upconversion luminescent "INHIBIT" and "OR" logic gates of water-dispersed CdTe quantum dots (QDs) were constituted by conjugating the QDs with dopamine. This facilitated the development of a novel QDs-based upconversion luminescent probe for efficient turn-on sensing of glutathione.

Sub-Band Gap Turn-On Near-Infrared-to-Visible Up-Conversion Device Enabled by an Organic-Inorganic Hybrid Perovskite Photovoltaic Absorber.

PubMed

Yu, By Hyeonggeun; Cheng, Yuanhang; Li, Menglin; Tsang, Sai-Wing; So, Franky

2018-05-09

Direct integration of an infrared (IR) photodetector with an organic light-emitting diode (OLED) enables low-cost, pixel-free IR imaging. However, the operation voltage of the resulting IR-to-visible up-conversion is large because of the series device architecture. Here, we report a low-voltage near-IR (NIR)-to-visible up-conversion device using formamidinium lead iodide as a NIR absorber integrated with a phosphorescent OLED. Because of the efficient photocarrier injection from the hybrid perovskite layer to the OLED, we observed a sub-band gap turn-on of the OLED under NIR illumination. The device showed a NIR-to-visible up-conversion efficiency of 3% and a luminance on/off ratio of 10 3 at only 5 V. Finally, we demonstrate pixel-free NIR imaging using the up-conversion device.

Sensitive Infrared Signal Detection by Upconversion Technique

NASA Technical Reports Server (NTRS)

Wong, Teh-Hwa; Yu, Jirong; Bai, Yingxin; Johnson, William; Chen, Songsheng; Petros, Mulugeta; Singh, Upendra N.

2014-01-01

We demonstrated upconversion assisted detection of a 2.05-micron signal by sum frequency generation to generate a 700-nm light using a bulk periodically poled lithium niobate crystal. The achieved 94% intrinsic upconversion efficiency and 22.58% overall detection efficiency at a pW level of 2.05 micron pave the path to detect extremely weak infrared (IR) signals for remote sensing applications.

Facile synthesis of hydrophilic multi-colour and upconversion photoluminescent mesoporous carbon nanoparticles for bioapplications.

PubMed

Kong, Qinglu; Zhang, Lingxia; Liu, Jianan; Wu, Meiying; Chen, Yu; Feng, Jingwei; Shi, Jianlin

2014-12-25

Hydrophilic mesoporous carbon nanoparticles (MCNs) have been synthesized via an extremely facile precursor carbonization-in-hot solvent route. The synthesized MCNs show well-defined particle and pore size distribution at around 100 nm and 2.7 nm, respectively, and multicolor and upconversion photoluminescence, which endow the MCNs with multicolor/upconversion bioimaging and drug delivery properties.

Infrared upconversion for astronomical applications. [laser applications to astronomical spectroscopy of infrared spectra

NASA Technical Reports Server (NTRS)

Abbas, M. M.; Kostiuk, T.; Ogilvie, K. W.

1975-01-01

The performance of an upconversion system is examined for observation of astronomical sources in the low to middle infrared spectral range. Theoretical values for the performance parameters of an upconversion system for astronomical observations are evaluated in view of the conversion efficiencies, spectral resolution, field of view, minimum detectable source brightness and source flux. Experimental results of blackbody measurements and molecular absorption spectrum measurements using a lithium niobate upconverter with an argon-ion laser as the pump are presented. Estimates of the expected optimum sensitivity of an upconversion device which may be built with the presently available components are given.

IR Image upconversion using band-limited ASE illumination fiber sources.

PubMed

Maestre, H; Torregrosa, A J; Capmany, J

2016-04-18

We study the field-of-view (FOV) of an upconversion imaging system that employs an Amplified Spontaneous Emission (ASE) fiber source to illuminate a transmission target. As an intermediate case between narrowband laser and thermal illumination, an ASE fiber source allows for higher spectral intensity than thermal illumination and still keeps a broad wavelength spectrum to take advantage of an increased non-collinear phase-matching angle acceptance that enlarges the FOV of the upconversion system when compared to using narrowband laser illumination. A model is presented to predict the angular acceptance of the upconverter in terms of focusing and ASE spectral width and allocation. The model is experimentally checked in case of 1550-630 nm upconversion.

Upconversion in solar cells

PubMed Central

2013-01-01

The possibility to tune chemical and physical properties in nanosized materials has a strong impact on a variety of technologies, including photovoltaics. One of the prominent research areas of nanomaterials for photovoltaics involves spectral conversion. Modification of the spectrum requires down- and/or upconversion or downshifting of the spectrum, meaning that the energy of photons is modified to either lower (down) or higher (up) energy. Nanostructures such as quantum dots, luminescent dye molecules, and lanthanide-doped glasses are capable of absorbing photons at a certain wavelength and emitting photons at a different (shorter or longer) wavelength. We will discuss upconversion by lanthanide compounds in various host materials and will further demonstrate upconversion to work for thin-film silicon solar cells. PMID:23413889

Activation of the surface dark-layer to enhance upconversion in a thermal field

NASA Astrophysics Data System (ADS)

Zhou, Jiajia; Wen, Shihui; Liao, Jiayan; Clarke, Christian; Tawfik, Sherif Abdulkader; Ren, Wei; Mi, Chao; Wang, Fan; Jin, Dayong

2018-03-01

Thermal quenching, in which light emission experiences a loss with increasing temperature, broadly limits luminescent efficiency at higher temperature in optical materials, such as lighting phosphors1-3 and fluorescent probes4-6. Thermal quenching is commonly caused by the increased activity of phonons that leverages the non-radiative relaxation pathways. Here, we report a kind of heat-favourable phonons existing at the surface of lanthanide-doped upconversion nanomaterials to combat thermal quenching. It favours energy transfer from sensitizers to activators to pump up the intermediate excited-state upconversion process. We identify that the oxygen moiety chelating Yb3+ ions, [Yb...O], is the key underpinning this enhancement. We demonstrate an approximately 2,000-fold enhancement in blue emission for 9.7 nm Yb3+-Tm3+ co-doped nanoparticles at 453 K. This strategy not only provides a powerful solution to illuminate the dark layer of ultra-small upconversion nanoparticles, but also suggests a new pathway to build high-efficiency upconversion systems.

One-step hydrothermal synthesis of carboxyl-functionalized upconversion phosphors for bioapplications.

PubMed

Yang, Jianping; Shen, Dengke; Li, Xiaomin; Li, Wei; Fang, Yin; Wei, Yong; Yao, Chi; Tu, Bo; Zhang, Fan; Zhao, Dongyuan

2012-10-22

In this paper, we report a facile one-step hydrothermal method to synthesize phase-, size-, and shape-controlled carboxyl-functionalized rare-earth fluorescence upconversion phosphors by using a small-molecule binary acid, such as malonic acid, oxalic acid, succinic acid, or tartaric acid as capping agent. The crystals, from nano- to microstructures with diverse shapes that include nanospheres, microrods, hexagonal prisms, microtubes, microdisks, polygonal columns, and hexagonal tablets, can be obtained with different reaction times, reaction temperatures, molar ratios of capping agent to sodium hydroxide, and by varying the binary acids. Fourier transform infrared, thermogravimetric analysis, and upconversion luminescence spectra measurements indicate that the synthesized NaYF(4):Yb/Er products with hydrophilic carboxyl-functionalized surface offer efficient upconversion luminescent performance. Furthermore, the antibody/secondary antibody conjugation can be realized by the carboxyl-functionalized surfaces of the upconversion phosphors, thus indicating the potential bioapplications of these kinds of materials. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Upconversion-Triggered Charge Separation in Polymer Semiconductors.

PubMed

Jang, Yu Jin; Kim, Eunah; Ahn, Seonghyeon; Chung, Kyungwha; Kim, Jihyeon; Kim, Heejun; Wang, Huan; Lee, Jiseok; Kim, Dong-Wook; Kim, Dong Ha

2017-01-19

Upconversion is a unique optical property that is driven by a sequential photon pumping and generation of higher energy photons in a consecutive manner. The efficiency improvement in photovoltaic devices can be achieved when upconverters are integrated since upconverters contribute to the generation of extra photons. Despite numerous experimental studies confirming the relationship, fundamental explanations for a real contribution of upconversion to photovoltaic efficiency are still in demand. In this respect, we suggest a new approach to visualize the upconversion event in terms of surface photovoltage (SPV) by virtue of Kelvin probe force microscopy (KPFM). One of the most conventional polymer semiconductors, poly(3-hexyl thiophene) (P3HT), is employed as a sensitizer to generate charge carriers by upconverted light. KPFM measurements reveal that the light upconversion enabled the formation of charge carriers in P3HT, resulting in large SPV of -54.9 mV. It confirms that the energy transfer from upconverters to P3HT can positively impact the device performance in organic solar cells (OSCs).

New anthracene derivatives as triplet acceptors for efficient green-to-blue low-power upconversion.

PubMed

Liang, Zuo-Qin; Sun, Bin; Ye, Chang-Qing; Wang, Xiao-Mei; Tao, Xu-Tang; Wang, Qin-Hua; Ding, Ping; Wang, Bao; Wang, Jing-Jing

2013-10-21

Three new anthracene derivatives [2-chloro-9,10-dip-tolylanthracene (DTACl), 9,10-dip-tolylanthracene-2-carbonitrile (DTACN), and 9,10-di(naphthalen-1-yl)anthracene-2-carbonitrile (DNACN)] were synthesized as triplet acceptors for low-power upconversion. Their linear absorption, single-photon-excited fluorescence, and upconversion fluorescence properties were studied. The acceptors exhibit high fluorescence yields in DMF. Selective excitation of the sensitizer Pd(II)octaethylporphyrin (PdOEP) in solution containing DTACl, DTACN, or DNA-CN at 532 nm with an ultralow excitation power density of 0.5 W cm(-2) results in anti-Stokes blue emission. The maximum upconversion quantum yield (Φ(UC) =17.4%) was obtained for the couple PdOEP/DTACl. In addition, the efficiency of the triplet-triplet energy transfer process was quantitatively studied by quenching experiments. Experimental results revealed that a highly effective acceptor for upconversion should combine high fluorescence quantum yields with efficient quenching of the sensitizer triplet. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Scalable Direct Writing of Lanthanide-Doped KMnF3 Perovskite Nanowires into Aligned Arrays with Polarized Up-Conversion Emission.

PubMed

Shi, Shuo; Sun, Ling-Dong; Xue, Ying-Xian; Dong, Hao; Wu, Ke; Guo, Shi-Chen; Wu, Bo-Tao; Yan, Chun-Hua

2018-05-09

The use of one-dimensional nano- and microstructured semiconductor and lanthanide materials is attractive for polarized-light-emission studies. Up-conversion emission from single-nanorod or anisotropic nanoparticles with a degree of polarization has also been discussed. However, microscale arrays of nanoparticles, especially well-aligned one-dimensional nanostructures as well as their up-conversion polarization characterization, have not been investigated yet. Herein, we present a novel and facile paradigm for preparing highly aligned arrays of lanthanide-doped KMnF 3 (KMnF 3 :Ln) perovskite nanowires, which are good candidates for polarized up-conversion emission studies. These perovskite nanowires, with a width of 10 nm and length of a few micrometers, are formed through the oriented attachment of KMnF 3 :Ln nanocubes along the [001] direction. By the employment of KMnF 3 :Ln nanowire gel as nanoink, a direct-writing method is developed to obtain diverse types of aligned patterns from the nanoscale to the wafer scale. Up-conversion emissions from the highly aligned nanowire arrays are polarized along the array direction with a polarization degree up to 60%. Taking advantage of microscopic nanowire arrays, these polarized up-conversion emissions should offer potential applications in light or information transportation.

Impurity doping: a novel strategy for controllable synthesis of functional lanthanide nanomaterials.

PubMed

Chen, Daqin; Wang, Yuansheng

2013-06-07

Many technological nanomaterials are intentionally 'doped' by introducing appropriate amounts of foreign elements into hosts to impart electronic, magnetic and optical properties. In fact, impurity doping was recently found to have significant influence on nucleation and growth of many functional nanocrystals (NCs), and provide a fundamental approach to modify the crystallographic phase, size, morphology, and electronic configuration of nanomaterials. In this feature article, we provide an overview of the most recent progresses in doping-induced control of phase structures, sizes, shapes, as well as performances of functional nanomaterials for the first time. Two kinds of impurity doping strategies, including the homo-valence ion doping and hetero-valence ion doping, are discussed in detail. We lay emphases on impurity doping induced modifications of microstructures and optical properties of upconversion (UC) lanthanide (Ln(3+)) NCs, but do not limit to them. In addition, we also illustrate the control of Ln(3+) activator distribution in the core@shell architecture, which has recently provided scientists with new opportunities for designing and tuning the multi-color emissions of Ln(3+)-doped UC NCs. Finally, the challenges and future perspectives of this novel impurity doping strategy are pointed out.

Preparation of ZnO nanoparticles showing upconversion luminescence through simple chemical method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anjana, R.; Subha, P. P.; Markose, Kurias K.

2016-05-23

Upconversion luminescence is an interesting area while considering its applications in a vast variety of fields. Rare earth ions like erbium is the most studied and efficient candidate for achieving upconversion. Erbium and ytterbium co-doped ZnO nanoparticles were prepared through co-precipitation method. A strong red emission has been obtained while exciting with 980 nm laser. Dependence of luminescence emission colour on ytterbium concentration has been studied.

Study of upconversion fluorescence property of novel Er3+/Yb3+ co-doped tellurite glasses.

PubMed

Xu, Tie-Feng; Li, Guang-Po; Nie, Qiu-Hua; Shen, Xiang

2006-06-01

Er3+/Yb3+ co-doped TeO2-B2O3-Nb2O5-ZnO (TBN) glasses were prepared. The absorption spectra and upconversion luminescence spectra of TBN glasses were measured and analyzed. The upconversion emission bands centered at 530, 546 and 658 nm were observed under the excitation at 975 nm, corresponding to the transitions of 2H11/2-->4I15/2, 4S3/2-->4I15/2 and 4F9/2-->4I15/2 respectively. The ratio of red emission to green emission increases with an increasing of Yb3+ ions concentration. According to the quadratic dependence on excitation power, the possible upconversion mechanisms and processes were discussed.

Active media for up-conversion diode-pumped lasers

NASA Astrophysics Data System (ADS)

Tkachuk, Alexandra M.

1996-03-01

In this work, we consider the different methods of populating the initial and final working levels of laser transitions in TR-doped crystals under the selective 'up-conversion' and 'avalanche' diode laser pumping. On the basis of estimates of the probabilities of competing non-radiative energy-transfer processes rates obtained from the experimental data and theoretical calculations, we estimated the efficiency of the up-conversion pumping and selfquenching of the upper TR3+ states excited by laser-diode emission. The effect of the host composition, dopant concentration, and temperature on the output characteristics and up-conversion processes in YLF:Er; BaY2F8:Er; BaY2F8:Er,Yb and BaY2F8:Yb,Ho are determined.

Effects of six different preventive treatments on the shear bond strength of orthodontic brackets: in vitro study.

PubMed

Cossellu, Gianguido; Lanteri, Valentina; Butera, Andrea; Sarcina, Michele; Farronato, Giampietro

2015-01-01

Objective : The aim of this study is to evaluate the effect of six different prophylactic agents on shear bond strength (SBS) of orthodontic brackets. Materials and methods : One hundred twenty-six freshly extracted mandibular bovine incisors were used. Teeth were randomly divided into 7 equal groups (18 per group) as follows: group-1 served as control with no pre-treatment; group-2 enamel treated with fluoride varnish (Fluor Protector, Ivoclar Vivadent); group-3 containing casein-phosphopeptide-amorphous calcium-phosphate (CPP-ACP) paste (GC Tooth Mousse, RECALDENT™); group-4 with ozone (HealOzone, Kavo ) ; group-5 with glycine powder (Perio Flow, EMS); group-6 with hydroxyapatite powder 99.5% (Coswell S.p.A.); group-7 with a toothpaste made of hydroxyapatite nanocrystals (BioRepair® Plus, Coswell S.p.A). Brackets were all bonded using the same technique with transbond XT (3 M Unitek, Monrovia, CA). All the bonded specimens were stored for 24 h in deionized water (37 °C) and subjected to thermal cycling for 1000 cycles. The SBS was measured with an Instron Universal Testing machine and the adhesive remnant was assessed with the adhesive remnant index (ARI) using a stereomicroscope at 10× magnification. Results : Statistical differences (ANOVA) were found among the seven investigated groups ( F = 12.226, p < 0.001). SBS of groups 2, 5 and 6 were significantly lower than the control group ( p < 0.05). ARI scores (chi-square test) were correlated with the differences of SBS values. Conclusion: CPP-ACP paste, ozone or BioRepair® did not compromise on bracket bond strength. Fluoride, glycine or hydroxyapatite significantly decreased the SBS; only the fluoride group showed significant clinically low (<6 MPa) SBS values.

Ultrafast fluorescence spectroscopy via upconversion applications to biophysics.

PubMed

Xu, Jianhua; Knutson, Jay R

2008-01-01

This chapter reviews basic concepts of nonlinear fluorescence upconversion, a technique whose temporal resolution is essentially limited only by the pulse width of the ultrafast laser. Design aspects for upconversion spectrophotofluorometers are discussed, and a recently developed system is described. We discuss applications in biophysics, particularly the measurement of time-resolved fluorescence spectra of proteins (with subpicosecond time resolution). Application of this technique to biophysical problems such as dynamics of tryptophan, peptides, proteins, and nucleic acids is reviewed.

Current advances in lanthanide ion (Ln(3+))-based upconversion nanomaterials for drug delivery.

PubMed

Yang, Dongmei; Ma, Ping'an; Hou, Zhiyou; Cheng, Ziyong; Li, Chunxia; Lin, Jun

2015-03-21

Lanthanide ion (Ln(3+))-based upconversion nano/micromaterials that emit higher-energy visible light when excited by low-energy NIR light have aroused considerable attention in the forefront of materials science and biomedical fields, which stems from their unique optical and chemical properties including minimum photodamage to living organisms, low autofluorescence, high signal-to-noise ratio and detection sensitivity, and high penetration depth in biological or environmental samples. Thus, Ln(3+)-based upconversion materials are rising new stars and are quickly emerging as potential candidates to revolutionize novel biomedical applications. In this review article, we mainly focus on the recent progress in various chemical syntheses of Ln(3+)-based upconversion nanomaterials, with special emphasis on their application in stimuli-response controlled drug release and subsequent therapy. Functional groups that are introduced into the stimuli-responsive system can respond to external triggers, such as pH, temperature, light, and even magnetic fields, which can regulate the movement of the pharmaceutical cargo and release the drug at a desired time and in a desired area. This is crucial to boost drug efficacy in cancer treatment while minimizing the side effects of cytotoxic drugs. Many multifunctional (magnetic/upconversion luminescence and porous) composite materials based on Ln(3+) have been designed for controlled drug delivery and multimodal bioimaging. Finally, the challenges and future opportunities for Ln(3+)-based upconversion materials are discussed.

Photon upconversion towards applications in energy conversion and bioimaging

NASA Astrophysics Data System (ADS)

Sun, Qi-C.; Ding, Yuchen C.; Sagar, Dodderi M.; Nagpal, Prashant

2017-12-01

The field of plasmonics can play an important role in developing novel devices for application in energy and healthcare. In this review article, we consider the progress made in design and fabrication of upconverting nanoparticles and metal nanostructures for precisely manipulating light photons, with a wavelength of several hundred nanometers, at nanometer length scales, and describe how to tailor their interactions with molecules and surfaces so that two or more lower energy photons can be used to generate a single higher energy photon in a process called photon upconversion. This review begins by introducing the current state-of-the-art in upconverting nanoparticle synthesis and achievements in color tuning and upconversion enhancement. Through understanding and tailoring physical processes, color tuning and strong upconversion enhancement have been demonstrated by coupling with surface plasmon polariton waves, especially for low intensity or diffuse infrared radiation. Since more than 30% of incident sunlight is not utilized in most photovoltaic cells, this photon upconversion is one of the promising approaches to break the so-called Shockley-Queisser thermodynamic limit for a single junction solar cell. Furthermore, since the low energy photons typically cover the biological window of optical transparency, this approach can also be particularly beneficial for novel biosensing and bioimaging techniques. Taken together, the recent research boosts the applications of photon upconversion using designed metal nanostructures and nanoparticles for green energy, bioimaging, and therapy.

Auger Up-Conversion of Low-Intensity Infrared Light in Engineered Quantum Dots

DOE PAGES

Makarov, Nikolay S.; Lin, Qianglu; Pietryga, Jeffrey M.; ...

2016-11-29

One source of efficiency losses in photovoltaic cells is their transparency toward solar photons with energies below the band gap of the absorbing layer. This loss can be reduced using a process of up-conversion whereby two or more sub-band-gap photons generate a single above-gap exciton. Traditional approaches to up-conversion, such as nonlinear two-photon absorption (2PA) or triplet fusion, suffer from low efficiency at solar light intensities, a narrow absorption bandwidth, nonoptimal absorption energies, and difficulties for implementing in practical devices. We show that these deficiencies can be alleviated using the effect of Auger up-conversion in thick-shell PbSe/CdSe quantum dots. Thismore » process relies on Auger recombination whereby two low-energy, core-based excitons are converted into a single higher-energy, shell-based exciton. When compared to their monocomponent counterparts, the tailored PbSe/CdSe heterostructures feature enhanced absorption cross-sections, a higher efficiency of the “productive” Auger pathway involving re-excitation of a hole, and longer lifetimes of both core- and shell-localized excitons. These features lead to effective up-conversion cross-sections that are more than 6 orders of magnitude higher than for standard nonlinear 2PA, which allows for efficient up-conversion of continuous wave infrared light at intensities as low as a few watts per square centimeter.« less

High-Temperature Surface Thermometry Technique based on Upconversion Nano-Phosphors

NASA Astrophysics Data System (ADS)

Combs, C.; Clemens, N.; Guo, X.; Song, H.; Zhao, H.; Li, K. K.; Zou, Y. K.; Jiang, H.

2011-11-01

Downconversion thermographic phosphors have been extensively used for high-temperature surface thermometry applications (e.g., aerothermodynamics, turbine blades) where temperature-sensitive paint is not viable. In downconversion techniques the phosphorescence is at longer wavelengths than the excitation source. We are developing a new upconversion thermographic phosphor technique that employs rare-earth-doped ceramics whose phosphorescence exhibit a strong temperature dependence. In the upconversion technique the phosphor is excited with near-IR light and emission is at visible wavelengths; thus, it does not require expensive UV windows and does not suffer from interference from background fluorescence. In this work the upconversion phosphors have been characterized in terms of their intensity, lifetimes and spectral content over a temperature range of 300K to 1500K. The technique has been evaluated for applications of 2D surface temperature measurements by using the total integrated intensity and the ratio of emission in different visible color bands. The results indicate that upconversion phosphor thermometry is a promising technique for making non-contact high-surface temperature measurements with good accuracy. Work supported by NASA under contract NNX11CG89P.

Two-step photon up-conversion solar cells

PubMed Central

Asahi, Shigeo; Teranishi, Haruyuki; Kusaki, Kazuki; Kaizu, Toshiyuki; Kita, Takashi

2017-01-01

Reducing the transmission loss for below-gap photons is a straightforward way to break the limit of the energy-conversion efficiency of solar cells (SCs). The up-conversion of below-gap photons is very promising for generating additional photocurrent. Here we propose a two-step photon up-conversion SC with a hetero-interface comprising different bandgaps of Al0.3Ga0.7As and GaAs. The below-gap photons for Al0.3Ga0.7As excite GaAs and generate electrons at the hetero-interface. The accumulated electrons at the hetero-interface are pumped upwards into the Al0.3Ga0.7As barrier by below-gap photons for GaAs. Efficient two-step photon up-conversion is achieved by introducing InAs quantum dots at the hetero-interface. We observe not only a dramatic increase in the additional photocurrent, which exceeds the reported values by approximately two orders of magnitude, but also an increase in the photovoltage. These results suggest that the two-step photon up-conversion SC has a high potential for implementation in the next-generation high-efficiency SCs. PMID:28382945

Enhancing Solar Cell Efficiency Using Photon Upconversion Materials

PubMed Central

Shang, Yunfei; Hao, Shuwei; Yang, Chunhui; Chen, Guanying

2015-01-01

Photovoltaic cells are able to convert sunlight into electricity, providing enough of the most abundant and cleanest energy to cover our energy needs. However, the efficiency of current photovoltaics is significantly impeded by the transmission loss of sub-band-gap photons. Photon upconversion is a promising route to circumvent this problem by converting these transmitted sub-band-gap photons into above-band-gap light, where solar cells typically have high quantum efficiency. Here, we summarize recent progress on varying types of efficient upconversion materials as well as their outstanding uses in a series of solar cells, including silicon solar cells (crystalline and amorphous), gallium arsenide (GaAs) solar cells, dye-sensitized solar cells, and other types of solar cells. The challenge and prospect of upconversion materials for photovoltaic applications are also discussed. PMID:28347095

Solid state photon upconversion utilizing thermally activated delayed fluorescence molecules as triplet sensitizer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Tony C.; Congreve, Daniel N.; Baldo, Marc A., E-mail: baldo@mit.edu

2015-07-20

The ability to upconvert light is useful for a range of applications, from biological imaging to solar cells. But modern technologies have struggled to upconvert incoherent incident light at low intensities. Here, we report solid state photon upconversion employing triplet-triplet exciton annihilation in an organic semiconductor, sensitized by a thermally activated-delayed fluorescence (TADF) dye. Compared to conventional phosphorescent sensitizers, the TADF dye maximizes the wavelength shift in upconversion due to its small singlet-triplet splitting. The efficiency of energy transfer from the TADF dye is 9.1%, and the conversion yield of sensitizer exciton pairs to singlet excitons in the annihilator ismore » 1.1%. Our results demonstrate upconversion in solid state geometries and with non-heavy metal-based sensitizer materials.« less

New nanoplatforms based on UCNPs linking with polyhedral oligomeric silsesquioxane (POSS) for multimodal bioimaging

NASA Astrophysics Data System (ADS)

Ge, Xiaoqian; Dong, Liang; Sun, Lining; Song, Zhengmei; Wei, Ruoyan; Shi, Liyi; Chen, Haige

2015-04-01

A new and facile method was used to transfer upconversion luminescent nanoparticles from hydrophobic to hydrophilic using polyhedral oligomeric silsesquioxane (POSS) linking on the surface of upconversion nanoparticles. In comparison with the unmodified upconversion nanoparticles, the POSS modified upconversion nanoplatforms [POSS-UCNPs(Er), POSS-UCNPs(Tm)] displayed good monodispersion in water and exhibited good water-solubility, while their particle size did not change substantially. Due to the low cytotoxicity and good biocompatibility as determined by methyl thiazolyl tetrazolium (MTT) assay and histology and hematology analysis, the POSS modified upconversion nanoplatforms were successfully applied to upconversion luminescence imaging of living cells in vitro and nude mouse in vivo (upon excitation at 980 nm). In addition, the doped Gd3+ ion endows the POSS-UCNPs with effective T1 signal enhancement and the POSS-UCNPs were successfully applied to in vivo magnetic resonance imaging (MRI) for a Kunming mouse, which makes them potential MRI positive-contrast agents. More importantly, the corner organic groups of POSS can be easily modified, resulting in kinds of POSS-UCNPs with many potential applications. Therefore, the method and results may provide more exciting opportunities for multimodal bioimaging and multifunctional applications.A new and facile method was used to transfer upconversion luminescent nanoparticles from hydrophobic to hydrophilic using polyhedral oligomeric silsesquioxane (POSS) linking on the surface of upconversion nanoparticles. In comparison with the unmodified upconversion nanoparticles, the POSS modified upconversion nanoplatforms [POSS-UCNPs(Er), POSS-UCNPs(Tm)] displayed good monodispersion in water and exhibited good water-solubility, while their particle size did not change substantially. Due to the low cytotoxicity and good biocompatibility as determined by methyl thiazolyl tetrazolium (MTT) assay and histology and hematology analysis, the POSS modified upconversion nanoplatforms were successfully applied to upconversion luminescence imaging of living cells in vitro and nude mouse in vivo (upon excitation at 980 nm). In addition, the doped Gd3+ ion endows the POSS-UCNPs with effective T1 signal enhancement and the POSS-UCNPs were successfully applied to in vivo magnetic resonance imaging (MRI) for a Kunming mouse, which makes them potential MRI positive-contrast agents. More importantly, the corner organic groups of POSS can be easily modified, resulting in kinds of POSS-UCNPs with many potential applications. Therefore, the method and results may provide more exciting opportunities for multimodal bioimaging and multifunctional applications. Electronic supplementary information (ESI) available: Schematic illustration of the formation of POSS-UCNPs. TEM images of NaYF4:Yb,Tm and NaYF4:Yb,Tm@NaGdF4 nanoparticles in cyclohexane; the TEM image of POSS-UCNPs(Tm) in water. DLS of POSS-UCNPs(Tm) in water. The energy dispersive X-ray (EDX) spectrum of POSS-UCNPs(Er). XPS of POSS-UCNPs(Er); XPS of Si element. UCL spectra of POSS-UCNPs(Er) in physiology saline as a function of time. UCL spectra of NaYF4:Yb,Tm@NaGdF4 [UCNPs(Tm)] and POSS-UCNPs(Tm), excited with a 980 nm laser (100 mW cm-2). In vivo UCL imaging of Kunming mice after intravenous injection with POSS-UCNPs(Tm) at different time points. See DOI: 10.1039/c5nr00950b

Ultrafast Fluorescence Spectroscopy via Upconversion: Applications to Biophysics

PubMed Central

Xu, Jianhua; Knutson, Jay R.

2012-01-01

This chapter reviews basic concepts of nonlinear fluorescence upconversion, a technique whose temporal resolution is essentially limited only by the pulse width of the ultrafast laser. Design aspects for upconversion spectrophotofluorometers are discussed, and a recently developed system is described. We discuss applications in biophysics, particularly the measurement of time-resolved fluorescence spectra of proteins (with subpicosecond time resolution). Application of this technique to biophysical problems such as dynamics of tryptophan, peptides, proteins, and nucleic acids is reviewed. PMID:19152860

Upconversion of Tm3+ ions in BaY2F8

NASA Astrophysics Data System (ADS)

Ruan, Yongfeng; Tsuboi, Taiju

1999-06-01

Up-conversion of red light with wavelength of 660 nm in Tm3+-doped BaY2F8 powder results in the two violet luminescence bands with peaks at 417 and 430 nm and two blue luminescence bands with peaks at 455 and 470 nm. The two violet bands are observed to be stronger than the blue bands. The blue luminescence is also observed by pumping with 993 nm light. The up-conversion is explained by a multiple excited state absorption process.

Up-conversion monodispersed spheres of NaYF4:Yb3+/Er3+: green and red emission tailoring mediated by heating temperature, and greatly enhanced luminescence by Mn2+ doping.

PubMed

Zhu, Qi; Song, Caiyun; Li, Xiaodong; Sun, Xudong; Li, Ji-Guang

2018-04-09

Submicron sized, monodispersed spheres of Mn2+, Yb3+/Er3+ and Mn2+/Yb3+/Er3+ doped α-NaYF4 were easily autoclaved from mixed solutions of the component nitrates and ammonium fluoride (NH4F), in the presence of EDTA-2Na. Detailed characterizations of the resultant phosphors were obtained using XRD, Raman spectroscopy, FE-SEM, HR-TEM, STEM, PLE/PL spectroscopy, and fluorescence decay analysis. Finer structure and better crystal perfection was observed at a higher calcination temperature, and the spherical shape and excellent dispersion of the original particles was retained at temperatures up to 600 °C. Under the 980 nm infrared excitation, the Yb3+/Er3+-doped sample (calcined at 400 °C) exhibits a stronger green emission centered at ∼524 nm (2H11/2 → 4I15/2 transition of Er3+) and a weaker red emission centered at ∼657 nm (4F9/2 → 4I15/2 transition of Er3+). A 200 °C increase in the temperature from 400 °C to 600 °C resulted in the dominant red emission originating from the 4F9/2 → 4I15/2 transition of Er3+, instead of the previously dominant green one. Mn2+ doping induced a remarkable more enhanced intensity at ∼657 nm and ∼667 nm (red emission area) than that at ∼524 nm and ∼546 nm (green emission area), because of the non-radiative energy transfer between Mn2+ and Er3+. However, a poor thermal stability was induced by Mn2+ doping. The observed upconversion luminescence of the samples calcined at 400 °C and 600 °C followed the two photon process and the four photon process, respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou Bo; Pun, Edwin Yue-Bun; Yang Dianlai

Ho{sup 3+}-doped and Ho{sup 3+}/Yb{sup 3+}-codoped lead bismuth gallate (PBG) oxide glasses were prepared and their spectroscopic properties were investigated. The derived Judd-Ofelt intensity parameters (OMEGA{sub 2}=6.81x10{sup -20} cm{sup 2}, OMEGA{sub 4}=2.31x10{sup -20} cm{sup 2}, and OMEGA{sub 6}=0.67x10{sup -20} cm{sup 2}) indicate a higher asymmetry and stronger covalent environment for Ho{sup 3+} sites in PBG glass compared with those in tellurite, fluoride (ZBLAN), and some other lead-contained glasses. Intense frequency upconversion emissions peaking at 547, 662, and 756 nm as well as infrared emissions at 1.20 and 2.05 mum in Ho{sup 3+}/Yb{sup 3+}-codoped PBG glass were observed, confirming that energymore » transfer between Yb{sup 3+} and Ho{sup 3+} takes place, and a two-phonon-assisted energy transfer from Yb{sup 3+} to Ho{sup 3+} ions was determined by the calculation using phonon sideband theory. The 1.20 mum emission observed was primarily due to the weak multiphonon deexcitation originated from the small phonon energy of PBG glass (approx535 cm{sup -1}). A large product of emission cross-section and measured lifetime (9.93x10{sup -25} cm{sup 2} s) was obtained for the 1.20 mum emission and the gain coefficient dependence on wavelength with population inversion rate (P) was performed. The peak emission cross-section for 2.05 mum emission was calculated to be 4.75x10{sup -21} cm{sup 2}. The relative mechanism of Ho{sup 3+}-doped and Ho{sup 3+}/Yb{sup 3+}-codoped PBG glasses on their spectroscopic properties was also discussed. Our results suggest that Ho{sup 3+}/Yb{sup 3+}-doped PBG glasses are a good potential candidate for the frequency upconversion devices and infrared amplifiers/lasers.« less

Synthetic and spectroscopic studies of vanadate glaserites I: Upconversion studies of doubly co-doped (Er, Tm, or Ho):Yb:K{sub 3}Y(VO{sub 4}){sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimani, Martin M., E-mail: kimani@g.clemson.edu; Chen, Hongyu, E-mail: hongyuc@g.clemson.edu; McMillen, Colin D., E-mail: cmcmill@g.clemson.edu

2015-03-15

The synthesis and upconversion properties of trigonal glaserite-type K{sub 3}Y(VO{sub 4}){sub 2} co-doped with Er{sup 3+}/Yb{sup 3+}, Ho{sup 3+}/Yb{sup 3+}, or Tm{sup 3+}/Yb{sup 3+} were studied. Powder samples were synthesized by solid state reactions at 1000 °C for 48 h, while well-formed hexagonal single crystals of the same were grown hydrothermally using 10 M K{sub 2}CO{sub 3} at 560–650 °C. Infrared-to-visible upconversion by Er{sup 3+}/Yb{sup 3+}, Ho{sup 3+}/Yb{sup 3+}, or Tm{sup 3+}/Yb{sup 3+} codoped-K{sub 3}Y(VO{sub 4}){sub 2} glaserite powder and single crystals was observed, and the upconversion spectral properties were studied as a function of different Er{sup 3+}, Tm{sup 3+},more » Ho{sup 3+}, and Yb{sup 3+} ion concentrations. The process is observed under 980 nm laser diode excitation and leads to strong green (552 nm) and red (659 nm) emission for Er{sup 3+}/Yb{sup 3+}, green (549 nm) and red (664 nm) emission for Ho{sup 3+}/Yb{sup 3+}, and blue (475 nm) and red (647 nm) emission for Tm{sup 3+}/Yb{sup 3+}. The main mechanism that allows for up-conversion is attributed the energy transfer among Yb{sup 3+} and the various Er{sup 3+}/Ho{sup 3+}/Tm{sup 3+} ions in excited states. These results illustrate the large potential of co-doped alkali double vanadates for photonic applications involving optoelectronics devices. - Graphical abstract: Synthesis and upconversion in vanadate glaserites. - Highlights: • K{sub 3}Y(VO{sub 4}){sub 2} codoped with Er, Tm, or Ho:Yb were synthesized via solid-state and hydrothermal routes. • Upconversion properties are investigated. • The codoped compounds revealed efficient infrared-to-visible upconversion. • The presented compounds are potential host for solid state lighting.« less

Nd3+, Yb3+ and Ho3+ Codoped Oxyfluoride Glass Ceramics with High Efficient Green Upconversion Luminescence

NASA Astrophysics Data System (ADS)

Zhang, Jun-Jie; Kawamoto, Yoji; Dai, Shi-Xun; Zhang, Li-Yan; Hu, Li-Li

2004-06-01

New oxyfluoride glasses and glass ceramic codoped with Nd3+, Yb3+ and Ho3+ were prepared. The x-ray diffraction analysis revealed that the heat treatments of the oxyfluoride glasses could cause the precipitation of (Nd3+, Yb3+, Ho3+)-doped fluorite-type crystals. Very strong green up-conversion luminescence due to the Ho3+: (5F4, 5S2)rightarrow5I8 transition under 800-nm excitation was observed in these transparent glass ceramics. The intensity of the green up-conversion luminescence in a 1-mol% YbF3-containing glass ceramic was found to be about 120 times stronger than that in the precursor oxyfluoride glass. The reason for the highly efficient Ho3+ up-conversion luminescence in the oxyfluoride glass ceramics is discussed.

Upconversion properties of Er3+/Yb3+ co-doped TeO2-TiO2-K2O glasses.

PubMed

Su, Fangning; Deng, Zaide

2006-01-01

The Er3+/Yb3+ co-doped TeO2-TiO2-K2O glasses were prepared by conventional melting procedures, and their upconversion spectra were performed. The dependence of luminescence intensity on the ratio of Yb3+/Er3+ was studied, and the relationship between green upconversion luminescence intensity and Er3+ concentration is discussed in detail. The 546 nm green upconversion luminescence intensity is optimised in the studied glasses either when the Yb3+/Er3+ ratio is 25/1 and Er3+ concentration is 0.1 mol%, or when the Yb3+/Er3+ ratio is 10/1 and Er3+ concentration is 0.15 mol%. These glasses could be one of the potential candidates for LD pumping microchip solid-state lasers.

Measuring upconversion nanoparticles photoluminescence lifetime with FastFLIM and phasor plots

NASA Astrophysics Data System (ADS)

Sun, Yuansheng; Lee, Hsien-Ming; Qiu, Hailin; Liao, Shih-Chu Jeff; Coskun, Ulas; Barbieri, Beniamino

2018-02-01

Photon upconversion is a nonlinear process in which the sequential of absorption of two or more photons leads to the anti-stoke emission. Different than the conventional multiphoton excitation process, upconversion can be efficiently performed at low excitation densities. Recent developments in lanthanide-doped upconversion nanoparticles (UCNPs) have led to a diversity of applications, including detecting and sensing of biomolecules, imaging of live cells, tissues and animals, cancer diagnostic and therapy, etc. Measuring the upconversion lifetime provides a new dimension of its imaging and opens a new window for its applications. Due to the long metastable intermediate excited state, UCNP typically has a long excited state lifetime ranging from sub-microseconds to milliseconds. Here, we present a novel development using the FastFLIM technique to measure UCNP lifetime by laser scanning confocal microscopy. FastFLIM is capable of measuring lifetime from 100 ps to 100 ms and features the high data collection efficiency (up to 140-million counts per second). Other than the traditional nonlinear least-square fitting analysis, the raw data acquired by FastFLIM can be directly processed by the model-free phasor plots approach for instant and unbiased lifetime results, providing the ideal routine for the UCNP photoluminescence lifetime microscopy imaging.

Frequency upconversion in Er3+ doped tungsten tellurite glass containing Ag nanoparticles

NASA Astrophysics Data System (ADS)

Mahajan, S. K.; Parashar, J.

2018-05-01

The frequency upconversion emission in Er3+ doped TeO2-WO3-Li2O containing Ag nanoparticle (TWLEOAG) glasses at 980nm excitation is reported. The absorption spectra reveal not only the peaks due to Er3+ ions, but also the surface plasmon resonance band of silver NPs located around 525nm and 650 nm. The spherical AgNPs with average size ˜38 nm in the glassy matrix is evidenced from the TEM measurement. Under 980nm laser excitation upconversion emission spectra show two major emission at 550nm and 638nm originating from 4S3/2 and 4F9/2 energy levels of the Er3+ ions, respectively was observed. Upconversion emission enhancement factor 7 fold has been measured for sample heat treated during 40h. However for 18h heat treated TWLEOAG sample under 980 nm flash lamp excitation produced Intense green compare to red emission. Since the 980nm frequency is far from the AgNPs surface plasmon resonance frequency, visible emission ehancement is attributed to local field increase in proximity of the Ag NPs and not energy tranfer from NPs to emitters. Possible energy transfer upconversion mechanism has been also discussed.

Limitations on the upconversion of ion sound to Langmuir turbulence

NASA Technical Reports Server (NTRS)

Vlahos, L.; Papadopoulos, K.

1982-01-01

The weak turbulence theory of Tsytovich, Stenflo and Wilhelmsson (1981) for evaluation of the nonlinear transfer of ion acoustic waves to Langmuir waves is shown to be limited in its region of validity to the level of ion acoustic waves. It is also demonstrated that, in applying the upconversion of ion sound to Langmuir waves for electron acceleration, nonlinear scattering should be self-consistently included, with a suppression of the upconversion process resulting. The impossibility of accelerating electrons by such a process for any reasonable physical system is thereby reaffirmed.

Photodegradation of near-infrared-pumped Tm(3+)-doped ZBLAN fiber upconversion lasers.

PubMed

Booth, I J; Archambault, J L; Ventrudo, B F

1996-03-01

Photodegradation has been observed in Tm(3+)-doped ZBLAN fiber lasers pumped with laser diodes at 1135 nm. After upconversion lasing at 482 nm, the fiber develops color centers that absorb strongly at wavelengths below ~650 nm, affecting further upconversion lasing. The rate of damage formation is strongly dependent on the pump power level and on the thulium concentration. The color centers are bleached by intense blue light but recover with thermal excitation and can be removed by thermal annealing at temperature near 100 degrees C.

Increasing conversion efficiency of two-step photon up-conversion solar cell with a voltage booster hetero-interface.

PubMed

Asahi, Shigeo; Kusaki, Kazuki; Harada, Yukihiro; Kita, Takashi

2018-01-17

Development of high-efficiency solar cells is one of the attractive challenges in renewable energy technologies. Photon up-conversion can reduce the transmission loss and is one of the promising concepts which improve conversion efficiency. Here we present an analysis of the conversion efficiency, which can be increased by up-conversion in a single-junction solar cell with a hetero-interface that boosts the output voltage. We confirm that an increase in the quasi-Fermi gap and substantial photocurrent generation result in a high conversion efficiency.

Ultralow noise up-conversion detector and spectrometer for the telecom band.

PubMed

Shentu, Guo-Liang; Pelc, Jason S; Wang, Xiao-Dong; Sun, Qi-Chao; Zheng, Ming-Yang; Fejer, M M; Zhang, Qiang; Pan, Jian-Wei

2013-06-17

We demonstrate up-conversion single-photon detection for the 1550-nm telecommunications band using a PPLN waveguide, long-wavelength pump, and narrowband filtering using a volume Bragg grating. We achieve total-system detection efficiency of around 30% with noise at the dark-count level of a Silicon APD. Based on the new detector, a single-pixel up-conversion infrared spectrometer with a noise equivalent power of -142 dBm Hz(-1/2) was demonstrated, which was as good as a liquid nitrogen cooled CCD camera.

Research progress of infrared detecting and display integrated device based on infrared-visible up-conversion technology

NASA Astrophysics Data System (ADS)

Xu, Junfeng; Li, Weile; He, Bo; Wang, Haowei; Song, Yong; Yang, Shengyi; Ni, Guoqiang

2018-01-01

Infrared detecting and display device (IR-DDD) is a newly developed optical up-conversion device that integrates the light-emitting diode (LED) onto the infrared (IR) photo-detector, in order to convert IR light into the carriers photo-generated in detection materials and inject them into LED to emit visible light. This IR-DDD can achieve the direct up-conversion from IR ray to visible light, showing the considerable potential in night-vision application. This paper attempts a review of its working principle and current research progresses.

Experimental demonstration of photon upconversion via cooperative energy pooling

DOE PAGES

Weingarten, Daniel H.; LaCount, Michael D.; van de Lagemaat, Jao; ...

2017-03-15

Photon upconversion is a fundamental interaction of light and matter that has applications in fields ranging from bioimaging to microfabrication. However, all photon upconversion methods demonstrated thus far involve challenging aspects, including requirements of high excitation intensities, degradation in ambient air, requirements of exotic materials or phases, or involvement of inherent energy loss processes. Here we experimentally demonstrate a mechanism of photon upconversion in a thin film, binary mixture of organic chromophores that provides a pathway to overcoming the aforementioned disadvantages. This singlet-based process, called Cooperative Energy Pooling (CEP), utilizes a sensitizer-acceptor design in which multiple photoexcited sensitizers resonantly andmore » simultaneously transfer their energies to a higher-energy state on a single acceptor. Data from this proof-of-concept implementation is fit by a proposed model of the CEP process. As a result, design guidelines are presented to facilitate further research and development of more optimized CEP systems.« less

Achieving high-efficiency emission depletion nanoscopy by employing cross relaxation in upconversion nanoparticles.

PubMed

Zhan, Qiuqiang; Liu, Haichun; Wang, Baoju; Wu, Qiusheng; Pu, Rui; Zhou, Chao; Huang, Bingru; Peng, Xingyun; Ågren, Hans; He, Sailing

2017-10-20

Stimulated emission depletion microscopy provides a powerful sub-diffraction imaging modality for life science studies. Conventionally, stimulated emission depletion requires a relatively high light intensity to obtain an adequate depletion efficiency through only light-matter interaction. Here we show efficient emission depletion for a class of lanthanide-doped upconversion nanoparticles with the assistance of interionic cross relaxation, which significantly lowers the laser intensity requirements of optical depletion. We demonstrate two-color super-resolution imaging using upconversion nanoparticles (resolution ~ 66 nm) with a single pair of excitation/depletion beams. In addition, we show super-resolution imaging of immunostained cytoskeleton structures of fixed cells (resolution ~ 82 nm) using upconversion nanoparticles. These achievements provide a new perspective for the development of photoswitchable luminescent probes and will broaden the applications of lanthanide-doped nanoparticles for sub-diffraction microscopic imaging.

Experimental demonstration of photon upconversion via cooperative energy pooling

PubMed Central

Weingarten, Daniel H.; LaCount, Michael D.; van de Lagemaat, Jao; Rumbles, Garry; Lusk, Mark T.; Shaheen, Sean E.

2017-01-01

Photon upconversion is a fundamental interaction of light and matter that has applications in fields ranging from bioimaging to microfabrication. However, all photon upconversion methods demonstrated thus far involve challenging aspects, including requirements of high excitation intensities, degradation in ambient air, requirements of exotic materials or phases, or involvement of inherent energy loss processes. Here we experimentally demonstrate a mechanism of photon upconversion in a thin film, binary mixture of organic chromophores that provides a pathway to overcoming the aforementioned disadvantages. This singlet-based process, called Cooperative Energy Pooling (CEP), utilizes a sensitizer-acceptor design in which multiple photoexcited sensitizers resonantly and simultaneously transfer their energies to a higher-energy state on a single acceptor. Data from this proof-of-concept implementation is fit by a proposed model of the CEP process. Design guidelines are presented to facilitate further research and development of more optimized CEP systems. PMID:28294129

Microwave hydrothermal synthesis and upconversion properties of Yb3+/Er3+ doped YVO4 nanoparticles

NASA Astrophysics Data System (ADS)

Kshetri, Yuwaraj K.; Regmi, Chhabilal; Kim, Hak-Soo; Wohn Lee, Soo; Kim, Tae-Ho

2018-05-01

Yb3+ and Er3+ doped YVO4 (Yb3+/Er3+:YVO4) nanoparticles with highly efficient near-infrared to visible upconversion properties have been synthesized by microwave hydrothermal process. Uniform-sized Yb3+/Er3+:YVO4 nanoparticles were synthesized within 1 h at 140 °C which is relatively faster than the conventional hydrothermal process. Under 980 nm laser excitation, strong green and less strong red emissions are observed which are attributed to 2H11/2, 4S3/2 to 4I15/2 and 4F9/2 to 4I15/2 transitions of Er3+ respectively. The emission intensity is found to depend strongly on the concentration of Yb3+. The quadratic dependence of upconversion intensity on the excitation power indicates that the upconversion process is governed by two-photon absorption process.

[Up-conversion luminescent materials of Y2O3: RE(RE=Er or Er/Yb) prepared by sol-gel combustion synthesis].

PubMed

Han, Peng-de; Zhang, Le; Huang, Xiao-gu; Wang, Li-xi; Zhang, Qi-tu

2010-11-01

Y2O3 powders doped with rare-earth ions were synthesized by sol-gel combustion synthesis. Effects of different calcinating temperatures, Er+ doping concentration and Yb3+ doping concentration were investigated. It was shown that the single well crystallized Y2O3 powders could be obtained at 800 degrees C; as the calcinating temperature increased, the crystallinity and upconversion luminescence intensity were higher; the particle size was uniform around 1 microm at 900 degrees C; when Er3+ doping concentration was 1 mol%, the green upconversion luminescence intensity reached the maximum, but for red upconversion luminescence, when Er3+ doping concentration was 4 mol%, its luminescence intensity reached the maximum; as the ratio of Yb3+ to Er3+ was 4:1, the green emission intensity reached the maximum, while the red emission intensity was always increasing as Yb3+ doping concentration increased.

Microwave hydrothermal synthesis and upconversion properties of Yb3+/Er3+ doped YVO4 nanoparticles.

PubMed

Kshetri, Yuwaraj K; Regmi, Chhabilal; Kim, Hak-Soo; Lee, Soo Wohn; Kim, Tae-Ho

2018-05-18

Yb 3+ and Er 3+ doped YVO 4 (Yb 3+ /Er 3+ :YVO 4 ) nanoparticles with highly efficient near-infrared to visible upconversion properties have been synthesized by microwave hydrothermal process. Uniform-sized Yb 3+ /Er 3+ :YVO 4 nanoparticles were synthesized within 1 h at 140 °C which is relatively faster than the conventional hydrothermal process. Under 980 nm laser excitation, strong green and less strong red emissions are observed which are attributed to 2 H 11/2 , 4 S 3/2 to 4 I 15/2 and 4 F 9/2 to 4 I 15/2 transitions of Er 3+ respectively. The emission intensity is found to depend strongly on the concentration of Yb 3+ . The quadratic dependence of upconversion intensity on the excitation power indicates that the upconversion process is governed by two-photon absorption process.

Single-band upconversion nanoprobes for multiplexed simultaneous in situ molecular mapping of cancer biomarkers.

PubMed

Zhou, Lei; Wang, Rui; Yao, Chi; Li, Xiaomin; Wang, Chengli; Zhang, Xiaoyan; Xu, Congjian; Zeng, Aijun; Zhao, Dongyuan; Zhang, Fan

2015-04-24

The identification of potential diagnostic markers and target molecules among the plethora of tumour oncoproteins for cancer diagnosis requires facile technology that is capable of quantitatively analysing multiple biomarkers in tumour cells and tissues. Diagnostic and prognostic classifications of human tumours are currently based on the western blotting and single-colour immunohistochemical methods that are not suitable for multiplexed detection. Herein, we report a general and novel method to prepare single-band upconversion nanoparticles with different colours. The expression levels of three biomarkers in breast cancer cells were determined using single-band upconversion nanoparticles, western blotting and immunohistochemical technologies with excellent correlation. Significantly, the application of antibody-conjugated single-band upconversion nanoparticle molecular profiling technology can achieve the multiplexed simultaneous in situ biodetection of biomarkers in breast cancer cells and tissue specimens and produce more accurate results for the simultaneous quantification of proteins present at low levels compared with classical immunohistochemical technology.

Optical Temperature Sensor Based on Infrared Excited Green Upconversion Emission in Hexagonal Phase NaLuF4:Yb3+/Er3+ Nanorods.

PubMed

Li, Dongyu; Tian, Linlin; Huang, Zhen; Shao, Lexi; Quan, Jun; Wang, Yuxiao

2016-04-01

Hexagonal phase NaLuF4:Yb3+/Er3+ nanorods were synthesized hydrothermally. An analysis of the intense green upconversion emissions at 525 nm and 550 nm in hexagonal phase NaLuF4:Yb3/+Er3+ nanorods under excitation power density of 4.2 W/cm2 available from a diode laser emitting at 976 nm, have been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive green upconversion emissions at 525 nm and 550 nm in this material was recorded in the physiological range from 295 to 343 K. The maximum sensitivity derived from the FIR technique of the green upconversion emissions is approximately 0.0044 K-1. Experimental results implied that hexagonal phase NaLuF4:Yb3/+Er3+ nanorods was a potential candidate for optical temperature sensor.

Triplet-triplet annihilation photon-upconversion: towards solar energy applications.

PubMed

Gray, Victor; Dzebo, Damir; Abrahamsson, Maria; Albinsson, Bo; Moth-Poulsen, Kasper

2014-06-14

Solar power production and solar energy storage are important research areas for development of technologies that can facilitate a transition to a future society independent of fossil fuel based energy sources. Devices for direct conversion of solar photons suffer from poor efficiencies due to spectrum losses, which are caused by energy mismatch between the optical absorption of the devices and the broadband irradiation provided by the sun. In this context, photon-upconversion technologies are becoming increasingly interesting since they might offer an efficient way of converting low energy solar energy photons into higher energy photons, ideal for solar power production and solar energy storage. This perspective discusses recent progress in triplet-triplet annihilation (TTA) photon-upconversion systems and devices for solar energy applications. Furthermore, challenges with evaluation of the efficiency of TTA-photon-upconversion systems are discussed and a general approach for evaluation and comparison of existing systems is suggested.

Intense upconversion luminescence and effect of local environment for Tm3+/Yb3+ co-doped novel TeO2-BiCl3 glass system.

PubMed

Wang, Guonian; Dai, Shixun; Zhang, Junjie; Wen, Lei; Yang, Jianhu; Jiang, Zhonghong

2006-05-15

We present the results of a study that uses theoretical and experimental methods to investigate the characteristics of the upconversion luminescence of Tm3+/Yb3+ codoped TeO2-BiCl3 glass system as a function of the BiCl3 fraction. These glasses are potentially important in the design of upconversion fiber lasers. Effect of local environment around Tm3+ on upconversion fluorescence intensity was analyzed by theoretical calculations. The structure and spectroscopic properties were investigated in the experiments by measuring the Raman spectra, IR transmission spectra, and absorption and fluorescence intensities at room temperature. The results indicate that blue luminescence quantum efficiency increases with increasing BiCl3 content from 10 to 60 mol%, which were interpreted by the increase of asymmetry of glass structure, decrease of phonon energy and removing of OH- groups.

Experimental demonstration of photon upconversion via cooperative energy pooling

NASA Astrophysics Data System (ADS)

Weingarten, Daniel H.; Lacount, Michael D.; van de Lagemaat, Jao; Rumbles, Garry; Lusk, Mark T.; Shaheen, Sean E.

2017-03-01

Photon upconversion is a fundamental interaction of light and matter that has applications in fields ranging from bioimaging to microfabrication. However, all photon upconversion methods demonstrated thus far involve challenging aspects, including requirements of high excitation intensities, degradation in ambient air, requirements of exotic materials or phases, or involvement of inherent energy loss processes. Here we experimentally demonstrate a mechanism of photon upconversion in a thin film, binary mixture of organic chromophores that provides a pathway to overcoming the aforementioned disadvantages. This singlet-based process, called Cooperative Energy Pooling (CEP), utilizes a sensitizer-acceptor design in which multiple photoexcited sensitizers resonantly and simultaneously transfer their energies to a higher-energy state on a single acceptor. Data from this proof-of-concept implementation is fit by a proposed model of the CEP process. Design guidelines are presented to facilitate further research and development of more optimized CEP systems.

Size-tunable and monodisperse Tm³⁺/Gd³⁺-doped hexagonal NaYbF₄ nanoparticles with engineered efficient near infrared-to-near infrared upconversion for in vivo imaging.

PubMed

Damasco, Jossana A; Chen, Guanying; Shao, Wei; Ågren, Hans; Huang, Haoyuan; Song, Wentao; Lovell, Jonathan F; Prasad, Paras N

2014-08-27

Hexagonal NaYbF4:Tm(3+) upconversion nanoparticles hold promise for use in high contrast near-infrared-to-near-infrared (NIR-to-NIR) in vitro and in vivo bioimaging. However, significant hurdles remain in their preparation and control of their morphology and size, as well as in enhancement of their upconversion efficiency. Here, we describe a systematic approach to produce highly controlled hexagonal NaYbF4:Tm(3+) nanoparticles with superior upconversion. We found that doping appropriate concentrations of trivalent gadolinium (Gd(3+)) can convert NaYbF4:Tm(3+) 0.5% nanoparticles with cubic phase and irregular shape into highly monodisperse NaYbF4:Tm(3+) 0.5% nanoplates or nanospheres in a pure hexagonal-phase and of tunable size. The intensity and the lifetime of the upconverted NIR luminescence at 800 nm exhibit a direct dependence on the size distribution of the resulting nanoparticles, being ascribed to the varied surface-to-volume ratios determined by the different nanoparticle size. Epitaxial growth of a thin NaYF4 shell layer of ∼2 nm on the ∼22 nm core of hexagonal NaYbF4:Gd(3+) 30%/Tm(3+) 0.5% nanoparticles resulted in a dramatic 350 fold NIR upconversion efficiency enhancement, because of effective suppression of surface-related quenching mechanisms. In vivo NIR-to-NIR upconversion imaging was demonstrated using a dispersion of phospholipid-polyethylene glycol (DSPE-PEG)-coated core/shell nanoparticles in phosphate buffered saline.

Size-Tunable and Monodisperse Tm3+/Gd3+-Doped Hexagonal NaYbF4 Nanoparticles with Engineered Efficient Near Infrared-to-Near Infrared Upconversion for In Vivo Imaging

PubMed Central

2015-01-01

Hexagonal NaYbF4:Tm3+ upconversion nanoparticles hold promise for use in high contrast near-infrared-to-near-infrared (NIR-to-NIR) in vitro and in vivo bioimaging. However, significant hurdles remain in their preparation and control of their morphology and size, as well as in enhancement of their upconversion efficiency. Here, we describe a systematic approach to produce highly controlled hexagonal NaYbF4:Tm3+ nanoparticles with superior upconversion. We found that doping appropriate concentrations of trivalent gadolinium (Gd3+) can convert NaYbF4:Tm3+ 0.5% nanoparticles with cubic phase and irregular shape into highly monodisperse NaYbF4:Tm3+ 0.5% nanoplates or nanospheres in a pure hexagonal-phase and of tunable size. The intensity and the lifetime of the upconverted NIR luminescence at 800 nm exhibit a direct dependence on the size distribution of the resulting nanoparticles, being ascribed to the varied surface-to-volume ratios determined by the different nanoparticle size. Epitaxial growth of a thin NaYF4 shell layer of ∼2 nm on the ∼22 nm core of hexagonal NaYbF4:Gd3+ 30%/Tm3+ 0.5% nanoparticles resulted in a dramatic 350 fold NIR upconversion efficiency enhancement, because of effective suppression of surface-related quenching mechanisms. In vivo NIR-to-NIR upconversion imaging was demonstrated using a dispersion of phospholipid-polyethylene glycol (DSPE-PEG)-coated core/shell nanoparticles in phosphate buffered saline. PMID:25027118

Strong upconversion from Er3Al5O12 ceramic powders prepared by low temperature direct combustion synthesis

NASA Astrophysics Data System (ADS)

Maciel, Glauco S.; Rakov, Nikifor; Fokine, Michael; Carvalho, Isabel C. S.; Pinheiro, Carlos B.

2006-08-01

Crystalline ceramic powders of Er3Al5O12 were obtained by low temperature direct combustion synthesis. Irradiating the sample with a low-power continuous-wave infrared (1.48μm) diode laser led to ultraviolet, violet, blue, green, and red (380, 410, 456, 495, 525, 550, and 660nm) emissions. The strong upconversion luminescence appeared to the eyes as an intense green color. The presence of efficient four- and three-photon frequency upconversion processes makes this material an excellent candidate for use in photonic devices based on upconverter phosphors.

Upconversion-based receivers for quantum hacking-resistant quantum key distribution

NASA Astrophysics Data System (ADS)

Jain, Nitin; Kanter, Gregory S.

2016-07-01

We propose a novel upconversion (sum frequency generation)-based quantum-optical system design that can be employed as a receiver (Bob) in practical quantum key distribution systems. The pump governing the upconversion process is produced and utilized inside the physical receiver, making its access or control unrealistic for an external adversary (Eve). This pump facilitates several properties which permit Bob to define and control the modes that can participate in the quantum measurement. Furthermore, by manipulating and monitoring the characteristics of the pump pulses, Bob can detect a wide range of quantum hacking attacks launched by Eve.

Yb3+ sensitized Tm3+ upconversion in tellurite lead oxide glass.

PubMed

Mohanty, Deepak Kumar; Rai, Vineet Kumar; Dwivedi, Y

2012-04-01

Triply ionized thulium/thulium--ytterbium doped/codoped TeO2-Pb3O4 (TPO) glasses have been fabricated by classical quenching method. The upconversion emission spectra in the Tm3+/Tm3+-Yb3+ doped/codoped glasses upon excitation with a diode laser lasing at ∼980 nm has been studied. Effect of the addition of the Yb3+ on the upconversion emission intensity in the visible and near infrared regions of the Tm3+ doped in TPO glass has been studied and the processes involved explored. Copyright © 2011 Elsevier B.V. All rights reserved.

Advances in highly doped upconversion nanoparticles.

PubMed

Wen, Shihui; Zhou, Jiajia; Zheng, Kezhi; Bednarkiewicz, Artur; Liu, Xiaogang; Jin, Dayong

2018-06-20

Lanthanide-doped upconversion nanoparticles (UCNPs) are capable of converting near-infra-red excitation into visible and ultraviolet emission. Their unique optical properties have advanced a broad range of applications, such as fluorescent microscopy, deep-tissue bioimaging, nanomedicine, optogenetics, security labelling and volumetric display. However, the constraint of concentration quenching on upconversion luminescence has hampered the nanoscience community to develop bright UCNPs with a large number of dopants. This review surveys recent advances in developing highly doped UCNPs, highlights the strategies that bypass the concentration quenching effect, and discusses new optical properties as well as emerging applications enabled by these nanoparticles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makarov, Nikolay S.; Lin, Qianglu; Pietryga, Jeffrey M.

One source of efficiency losses in photovoltaic cells is their transparency toward solar photons with energies below the band gap of the absorbing layer. This loss can be reduced using a process of up-conversion whereby two or more sub-band-gap photons generate a single above-gap exciton. Traditional approaches to up-conversion, such as nonlinear two-photon absorption (2PA) or triplet fusion, suffer from low efficiency at solar light intensities, a narrow absorption bandwidth, nonoptimal absorption energies, and difficulties for implementing in practical devices. We show that these deficiencies can be alleviated using the effect of Auger up-conversion in thick-shell PbSe/CdSe quantum dots. Thismore » process relies on Auger recombination whereby two low-energy, core-based excitons are converted into a single higher-energy, shell-based exciton. When compared to their monocomponent counterparts, the tailored PbSe/CdSe heterostructures feature enhanced absorption cross-sections, a higher efficiency of the “productive” Auger pathway involving re-excitation of a hole, and longer lifetimes of both core- and shell-localized excitons. These features lead to effective up-conversion cross-sections that are more than 6 orders of magnitude higher than for standard nonlinear 2PA, which allows for efficient up-conversion of continuous wave infrared light at intensities as low as a few watts per square centimeter.« less

The effect of micro-structure on upconversion luminescence of Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glass-ceramics

NASA Astrophysics Data System (ADS)

Zhang, Minghui; Wen, Haiqin; Pan, Xiuhong; Yu, Jianding; Jiang, Meng; Yu, Huimei; Tang, Meibo; Gai, Lijun; Ai, Fei

2018-03-01

Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glasses have been prepared by aerodynamic levitation method. The glasses show high refractive index of 2.28 and Abbe number of 18.3. Glass-ceramics heated at 880 °C for 50 min perform the strongest upconversion luminescence. X-ray diffraction patterns of glass-ceramics with different depths indicate that rare earth ions restrain crystallization. Body crystallization mechanism mixed with surface crystallization is confirmed in the heat treatment. Surface crystals achieve priority to grow, resulting in important effects on upconversion luminescence. The results of atomic force microscope and scanning electron microscope indicate that crystal particles with uniform size distribute densely and homogenously on the surface and large amount of glass matrix exists in the glass ceramics heated at 880 °C for 50 min. Crystals in the glass-ceramics present dense structure and strong boundaries, which can reduce the mutual nonradiative relaxation rate among rare earth ions and then improve upconversion luminescence effectively. Based on micro-structural study, the mechanism that upconversion luminescence can be improved by heat treatment has been revealed. The results of micro-structural analysis agree well with the spectra.

Perspectives and challenges of photon-upconversion nanoparticles - Part I: routes to brighter particles and quantitative spectroscopic studies.

PubMed

Resch-Genger, Ute; Gorris, Hans H

2017-10-01

Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been the focus of many research activities in materials and life sciences in the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. To fully exploit the application potential of these fascinating nanomaterials, a number of challenges have to be overcome, such as the low brightness, particularly of small UCNPs, and the reliable quantification of the excitation-power-density-dependent upconversion luminescence. In this series of critical reviews, recent developments in the design, synthesis, optical-spectroscopic characterization, and application of UCNPs are presented with special focus on bioanalysis and the life sciences. Here we guide the reader from the synthesis of UCNPs to different concepts to enhance their luminescence, including the required optical-spectroscopic assessment to quantify material performance; surface modification strategies and bioanalytical applications as well as selected examples of the use of UCNPs as reporters in different assay formats are addressed in part II. Future trends and challenges in the field of upconversion are discussed with special emphasis on UCNP synthesis and material characterization, particularly quantitative luminescence studies. Graphical Abstract Both synthesis and spectroscopy as well bioanalytical applications of UCNPs are driven and supported by COST Action CM1403 "The European Upconversion Network".

Spectroscopic Imaging of NIR to Visible Upconversion from NaYF4:Yb3+, Er3+ Nanoparticles on Au Nano-cavity Arrays

NASA Astrophysics Data System (ADS)

Fisher, Jon; Zhao, Bo; Lin, Cuikun; Berry, Mary; May, P. Stanley; Smith, Steve

2015-03-01

We use spectroscopic imaging to assess the spatial variations in upconversion luminescence from NaYF4:Er3+,Yb3+ nanoparticles embedded in PMMA on Au nano-cavity arrays. The nano-cavity arrays support a surface plasmon (SP) resonance at 980nm, coincident with the peak absorption of the Yb3+ sensitizer. Spatially-resolved upconversion spectra show a 30X to 3X luminescence intensity enhancement on the nano-cavity array compared to the nearby smooth Au surface, corresponding to excitation intensities from 1 W/cm2 to 300kW/cm2. Our analysis shows the power dependent enhancement in upconversion luminescence can be almost entirely accounted for by a constant shift in the effective excitation intensity, which is maintained over five orders of magnitude variation in excitation intensity. The variations in upconversion luminescence enhancement with power are modeled by a 3-level-system near the saturation limit, and by simultaneous solution of a system of coupled nonlinear differential equations, both analyses agree well with the experiments. Analysis of the statistical distribution of emission intensities in the spectroscopic images on and off the nano-cavity arrays provides an estimate of the average enhancement factor independent of fluctuations in nano-particle density. Funding provided by NSF Award # 0903685 (IGERT).

NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} core/shell nanocomposite: A highly efficient visible-light-driven photocatalyst utilizing upconversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yuanyuan; Wang, Wenzhong, E-mail: wzwang@mail.sic.ac.cn; Sun, Songmei

2014-04-01

Highlights: • Design and synthesis of NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} based on upconversion. • NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} nanocomposite was prepared for the first time. • Core–shell structure benefits the properties. • Upconversion contributed to the enhanced photocatalytic activity. • Helps to understand the functionality of new type photocatalysts. - Abstract: NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} core/shell nanocomposite was designed and prepared for the first time based on upconversion. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution TEM (HRTEM), energy dispersive X-ray spectroscopy (EDS) and diffuse reflectance spectra (DRS). The results revealed that the as-synthesizedmore » NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} consisted of spheres with a core diameter of about 26 nm and a shell diameter of around 6 nm. The core was upconversion illuminant NaYF{sub 4}:Er,Yb and the shell was Bi{sub 2}MoO{sub 6} around the core, which was confirmed by EDS. The NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} exhibited higher photocatalytic activity for the photodecomposition of Rhodamine B (RhB) under the irradiation of Xe lamp and green light emitting diode (g-LED). The mechanism of the high photocatalytic activity was discussed by photoluminescence spectra (PL), which is mainly attributed to upconversion of NaYF{sub 4}:Er,Yb in the NaYF{sub 4}:Er,Yb/Bi{sub 2}MoO{sub 6} nanocomposite and the core–shell structure.« less

Enhanced Power Conversion Efficiency of Perovskite Solar Cells with an Up-Conversion Material of Er3+-Yb3+-Li+ Tri-doped TiO2

NASA Astrophysics Data System (ADS)

Zhang, Zhenlong; Qin, Jianqiang; Shi, Wenjia; Liu, Yanyan; Zhang, Yan; Liu, Yuefeng; Gao, Huiping; Mao, Yanli

2018-05-01

In this paper, Er3+-Yb3+-Li+ tri-doped TiO2 (UC-TiO2) was prepared by an addition of Li+ to Er3+-Yb3+ co-doped TiO2. The UC-TiO2 presented an enhanced up-conversion emission compared with Er3+-Yb3+ co-doped TiO2. The UC-TiO2 was applied to the perovskite solar cells. The power conversion efficiency (PCE) of the solar cells without UC-TiO2 was 14.0%, while the PCE of the solar cells with UC-TiO2 was increased to 16.5%, which presented an increase of 19%. The results suggested that UC-TiO2 is an effective up-conversion material. And this study provided a route to expand the spectral absorption of perovskite solar cells from visible light to near-infrared using up-conversion materials.

NIR-to-visible upconversion nanoparticles for fluorescent labeling and targeted delivery of siRNA

NASA Astrophysics Data System (ADS)

Jiang, Shan; Zhang, Yong; Lim, Kian Meng; Sim, Eugene K. W.; Ye, Lei

2009-04-01

Near-infrared (NIR)-to-visible upconversion fluorescent nanoparticles were synthesized and used for imaging and targeted delivery of small interfering RNA (siRNA) to cancer cells. Silica-coated NaYF4 upconversion nanoparticles (UCNs) co-doped with lanthanide ions (Yb/Er) were synthesized. Folic acid and anti-Her2 antibody conjugated UCNs were used to fluorescently label the folate receptors of HT-29 cells and Her2 receptors of SK-BR-3 cells, respectively. The intracellular uptake of the folic acid and antibody conjugated UCNs was visualized using a confocal fluorescence microscope equipped with an NIR laser. siRNA was attached to anti-Her2 antibody conjugated UCNs and the delivery of these nanoparticles to SK-BR-3 cells was studied. Meanwhile, a luciferase assay was established to confirm the gene silencing effect of siRNA. Upconversion nanoparticles can serve as a fluorescent probe and delivery system for simultaneous imaging and delivery of biological molecules.

Self-assembly of an upconverting nanocomplex and its application to turn-on detection of metalloproteinase-9 in living cells

NASA Astrophysics Data System (ADS)

Nguyen, Phuong-Diem; Thanh Cong, Vu; Baek, Changyoon; Min, Junhong

2016-10-01

Upcoversion nanoparticles are an emerging luminescent nanomaterial with excellent photophysical properties that have great benefits in biological sensing. In this study, a luminescent turn-on biosensor for cell-secreted protease activity assay is established based on resonance energy transfer in an upconversion nanoparticle-graphene oxide nano-assembly. The proposed biosensor consists of a blue-emitting upconversion nanoparticle covered with a quenching complex, comprising gelatin as the proteinase substrate and graphene oxide nanosheets as luminescence acceptors. After enzymatic digestion, the upconversion nanoparticles lose the gelatin cover due to the disassembly of the quenching complex, thus the upconverting luminescence in the blue region is restored (a turn-on response). The recovered upconverting luminescence is proportional to the protease concentration; the limit of detection was 12 ng ml-1. Finally, the upconversion-graphene oxide nanocomplex was successfully applied in the detection of cell-secreted protease-metalloproteinase in MCF-7 cancer cells with high sensitivity and specificity.

Security writing application of thermal decomposition assisted NaYF4:Er3+/Yb3+ upconversion phosphor

NASA Astrophysics Data System (ADS)

Kumar, A.; Tiwari, S. P.; Esteves da Silva, Joaquim C. G.; Kumar, K.

2018-07-01

The authors have synthesized water-dispersible NaYF4:Er3+/Yb3+ upconversion particles via a thermal decomposition route and optimized the green upconversion emission through a concentration variation of the Yb3+ sensitizer. The prepared particles were found to be ellipsoid in shape having an average particle dimension of 600  ×  150 nm. It is observed that the sample with 18 mmol% Yb3+ ion concentration and 2 mmol% Er3+ ion gives optimum upconversion intensity in the green region under 980 nm excitation. Colloidal dispersibility of the sample in different solvents was checked and hexane was found to be the best medium for the prepared particles. The particle size of the sample was found to be suitable for the preparation of colloidal ink and security writing on a plain sheet of paper. This was demonstrated successfully using ink prepared in polyvinyl chloride gold medium.

Enhanced Power Conversion Efficiency of Perovskite Solar Cells with an Up-Conversion Material of Er3+-Yb3+-Li+ Tri-doped TiO2.

PubMed

Zhang, Zhenlong; Qin, Jianqiang; Shi, Wenjia; Liu, Yanyan; Zhang, Yan; Liu, Yuefeng; Gao, Huiping; Mao, Yanli

2018-05-11

In this paper, Er 3+ -Yb 3+ -Li + tri-doped TiO 2 (UC-TiO 2 ) was prepared by an addition of Li + to Er 3+ -Yb 3+ co-doped TiO 2 . The UC-TiO 2 presented an enhanced up-conversion emission compared with Er 3+ -Yb 3+ co-doped TiO 2 . The UC-TiO 2 was applied to the perovskite solar cells. The power conversion efficiency (PCE) of the solar cells without UC-TiO 2 was 14.0%, while the PCE of the solar cells with UC-TiO 2 was increased to 16.5%, which presented an increase of 19%. The results suggested that UC-TiO 2 is an effective up-conversion material. And this study provided a route to expand the spectral absorption of perovskite solar cells from visible light to near-infrared using up-conversion materials.

Integrated optical modulator for signal up-conversion over radio-on-fiber link.

PubMed

Kim, Woo-Kyung; Kwon, Soon-Woo; Jeong, Woo-Jin; Son, Geun-Sik; Lee, Kwang-Hyun; Choi, Woo-Young; Yang, Woo-Seok; Lee, Hyung-Man; Lee, Han-Young

2009-02-16

An integrated optical modulator, which consists of a dual-sideband suppressed carrier (DSB-SC) modulator cascaded with a single-sideband (SSB) modulator, is proposed for signal up-conversion over Radio-on-Fiber. Utilizing a single-drive domain inverted structure in both modulators, balanced modulations were obtained without complicated radio frequency (RF) driving circuits and delicate RF phase adjustments. Intermediate frequency (IF) band signal was up-conversed to 60GHz band by using the fabricated device and was transmitted over optical fiber. Experiment results show that the proposed device enables millimeter wave generation and signal transmission without any power penalty caused by chromatic dispersion.

1.5- μm single photon counting using polarization-independent up-conversion detector

NASA Astrophysics Data System (ADS)

Takesue, Hiroki; Diamanti, Eleni; Langrock, Carsten; Fejer, M. M.; Yamamoto, Yoshihisa

2006-12-01

We report a 1.5- μm band polarization independent single photon detector based on frequency up-conversion in periodically poled lithium niobate (PPLN) waveguides. To overcome the polarization dependence of the PPLN waveguides, we employed a polarization diversity configuration composed of two up-conversion detectors connected with a polarization beam splitter. We experimentally confirmed polarization independent single photon counting using our detector. We undertook a proof-of-principle differential phase shift quantum key distribution experiment using the detector, and confirmed that the sifted key rate and error rate remained stable when the polarization state was changed during single photon transmission.

Exploiting the benefit of S0 → T1 excitation in triplet-triplet annihilation upconversion to attain large anti-stokes shifts: tuning the triplet state lifetime of a tris(2,2'-bipyridine) osmium(ii) complex.

PubMed

Liu, Dongyi; Zhao, Yingjie; Wang, Zhijia; Xu, Kejing; Zhao, Jianzhang

2018-03-07

Os(ii) complexes are particularly interesting for triplet-triplet annihilation (TTA) upconversion, due to the strong direct S 0 → T 1 photoexcitation, as in this way, energy loss is minimized and large anti-Stokes shift can be achieved for TTA upconversion. However, Os(bpy) 3 has an intrinsic short T 1 state lifetime (56 ns), which is detrimental for the intermolecular triplet-triplet energy transfer (TTET), one of the crucial steps in TTA upconversion. In order to prolong the triplet state lifetime, we prepared an Os(ii) tris(bpy) complex with a Bodipy moiety attached, so that an extended T 1 state lifetime is achieved by excited state electronic configuration mixing or triplet state equilibrium between the coordination center-localized state ( 3 MLCT state) and Bodipy ligand-localized state ( 3 IL state). With steady-state and time-resolved transient absorption/emission spectroscopy, we proved that the 3 MLCT is slightly above the 3 IL state (by 0.05 eV), and the triplet state lifetime was prolonged by 31-fold (from 56 ns to 1.73 μs). The TTA upconversion quantum yield was increased by 4-fold as compared to that of the unsubstituted Os(ii) complex.

[Two-photon up-conversion fluorescence of a neodymium organic framework Nd(BTC)].

PubMed

Xu, Hui; Jin, Run-zhi; Wu, Chun-yang; Yang, Yu; Qian, Guo-dong

2008-08-01

In the present work, a neodymium organic framework Nd(BTC) was synthesized by the solvothermal reaction of Nd(NO3)3 x 5H2O and H3BTC (BTC = 1,3,5-benzenetricarboxylate) in mixed solvents of DMF, ethanol and water, and was identified by elemental analysis. This MOF complex was characterized using X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TGA-DSC) analysis, UV-visible absorption spectra and fluorescence spectra. This polycrystalline powder lost DMF and H2O when heated to 120 degrees C, then remained stable till the temperature reached 500 degrees C. Near infrared fluorescence at 1064 nm due to the 4 F3/2--> 4 I11/2 transition of Nd3+ ions was exhibited when excited by 808 nm laser beam. It was also been found that up-conversion fluorescence of Nd(BTC) peaked at about 450 nm due to 2 D5/2 -->4 I11/2 transition of Nd3+ ions can be observed under the excitation of a 580 nm laser line. The mechanism of the up-conversion fluorescence of Nd(BTC) at around 450 nm under the excitation of 580 nm laser can be ascribed to both excited-state absorption and energy transfer up-conversion. This result indicated that such MOF can be employed as an up-conversion luminescence material in many potential application areas such as bio-labeling and fluorescence image.

Photochemical Upconversion: A Physical or Inorganic Chemistry Experiment for Undergraduates Using a Conventional Fluorimeter

ERIC Educational Resources Information Center

Wilke, Bryn M.; Castellano, Felix N.

2013-01-01

Photochemical upconversion is a regenerative process that transforms lower-energy photons into higher-energy light through two sequential bimolecular reactions, triplet sensitization of an appropriate acceptor followed by singlet fluorescence producing triplet-triplet annihilation derived from two energized acceptors. This laboratory directly…

The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes

NASA Astrophysics Data System (ADS)

Sojka, Bartlomiej; Liskova, Aurelia; Kuricova, Miroslava; Banski, Mateusz; Misiewicz, Jan; Dusinska, Maria; Horvathova, Mira; Ilavska, Silvia; Szabova, Michaela; Rollerova, Eva; Podhorodecki, Artur; Tulinska, Jana

2017-02-01

Sodium fluoride-based β-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of <10-nm NPs was performed according to our variation of patent pending ligand exchange method that resulted in meso-2,3-dimercaptosuccinic acid (DMSA) molecules on their surface. Y-core-based NCs were doped with Eu ions, which enabled them to be excited with UV light wavelengths. Cultures of human peripheral blood ( n = 8) were in vitro treated with five different concentrations of eight NPs for 24 h. In summary, neither type of nanoparticles is found toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.

Color-tunable up-conversion emission in Y2O3:Yb3+, Er3+ nanoparticles prepared by polymer complex solution method

PubMed Central

2013-01-01

Abstract Powders of Y2O3 co-doped with Yb3+ and Er3+ composed of well-crystallized nanoparticles (30 to 50 nm in diameter) with no adsorbed ligand species on their surface are prepared by polymer complex solution method. These powders exhibit up-conversion emission upon 978-nm excitation with a color that can be tuned from green to red by changing the Yb3+/Er3+ concentration ratio. The mechanism underlying up-conversion color changes is presented along with material structural and optical properties. PACS 42.70.-a, 78.55.Hx, 78.60.-b PMID:23522083

Optical transitions of Ho(3+) in oxyfluoride glasses and upconversion luminescence of Ho(3+)/Yb(3+)-codoped oxyfluoride glasses.

PubMed

Feng, Li; Wu, Yinsu

2015-05-05

Optical properties of Ho(3+)-doped SiO2-BaF2-ZnF2 glasses have been investigated on the basis of the Judd-Ofelt theory. Judd-Ofelt intensity parameters, radiative transition probabilities, fluorescence branching ratios and radiative lifetimes have been calculated for different glass compositions. Upconversion emissions were observed in Ho(3+)/Yb(3+)-codoped SiO2-BaF2-ZnF2 glasses under 980nm excitation. The effects of composition, concentration of the doping ions, and excitation pump power on the upconversion emissions were also systematically studied. Copyright © 2015 Elsevier B.V. All rights reserved.

Optical transitions of Tm3+ in oxyfluoride glasses and compositional and thermal effect on upconversion luminescence of Tm3+/Yb3+-codoped oxyfluoride glasses.

PubMed

Feng, Li; Wu, Yinsu; Liu, Zhuo; Guo, Tao

2014-01-24

Optical properties of Tm(3+)-doped SiO2-BaF2-ZnF2 glasses have been investigated on the basis of the Judd-Ofelt theory. Judd-Ofelt intensity parameters, radiative transition probabilities, fluorescence branching ratios and radiative lifetimes have been calculated for different glass compositions. Upconversion emissions were observed in Tm(3+)/Yb(3+)-codoped SiO2-BaF2-ZnF2 glasses under 980 nm excitation. The effects of composition, concentration of the doping ions, temperature, and excitation pump power on the upconversion emissions were also systematically studied. Copyright © 2013 Elsevier B.V. All rights reserved.

Luminescence of Er/Yb and Tm/Yb doped FAp nanoparticles and ceramics

NASA Astrophysics Data System (ADS)

Grigorjeva, L.; Smits, K.; Millers, D.; Jankoviča, Dz

2015-03-01

The nanoparticles of hydroxiapatite and fluorapatite doped with Er/Yb and Tm/Yb were synthesized and characterized by FTIR, XRD, SEM and TEM methods. The results of up-conversion luminescence studies were presented for the samples as prepared, annealed at 500°C and at 900-1000 °C. At annealing above 800°C the ceramic state was formed. It is shown that fluorapatite host is more appropriate than hydroxiapatite host for rare ions luminescence and up-conversion processes. The post preparing annealing of nanarticles significantly enhanced the luminescence intensity. The Tm/Yb doped fluorapatite shows intense up-conversion luminescence in 790-800 nm spectral region and is potentially useful for biomedical applications.

Up-conversion of MMW radiation to visual band using glow discharge detector and silicon detector

NASA Astrophysics Data System (ADS)

Aharon Akram, Avihai; Rozban, Daniel; Abramovich, Amir; Yitzhaky, Yitzhak; Kopeika, Natan S.

2016-10-01

In this work we describe and demonstrate a method for up-conversion of millimeter wave (MMW) radiation to the visual band using a very inexpensive miniature Glow Discharge Detector (GDD), and a silicon detector (photodetector). Here we present 100 GHz up-conversion images based on measuring the visual light emitting from the GDD rather than its electrical current. The results showed better response time of 480 ns and better sensitivity compared to the electronic detection that was performed in our previous work. In this work we performed MMW imaging based on this method using a GDD lamp, and a photodetector to measure GDD light emission.

808 nm-excited upconversion nanoprobes with low heating effect for targeted magnetic resonance imaging and high-efficacy photodynamic therapy in HER2-overexpressed breast cancer.

PubMed

Zeng, Leyong; Pan, Yuanwei; Zou, Ruifen; Zhang, Jinchao; Tian, Ying; Teng, Zhaogang; Wang, Shouju; Ren, Wenzhi; Xiao, Xueshan; Zhang, Jichao; Zhang, Lili; Li, Aiguo; Lu, Guangming; Wu, Aiguo

2016-10-01

To avoid the overheating effect of excitation light and improve the efficacy of photodynamic therapy (PDT) of upconversion nanoplatform, a novel nanoprobe based on 808 nm-excited upconversion nanocomposites (T-UCNPs@Ce6@mSiO2) with low heating effect and deep penetration has been successfully constructed for targeted upconversion luminescence, magnetic resonance imaging (MRI) and high-efficacy PDT in HER2-overexpressed breast cancer. In this nanocomposite, photosensitizers (Ce6) were covalently conjugated inside of mesoporous silica to enhance the PDT efficacy by shortening the distance of fluorescence resonance energy transfer and to decrease the cytotoxicity by preventing the undesired leakage of Ce6. Compared with UCNPs@mSiO2@Ce6, UCNPs@Ce6@mSiO2 greatly promoted the singlet oxygen generation and amplified the PDT efficacy under the excitation of 808 nm laser. Importantly, the designed nanoprobe can greatly improve the uptake of HER2-positive cells and tumors by modifying the site-specific peptide, and the in vivo experiments showed excellent MRI and PDT via intravenous injection by modeling MDA-MB-435 tumor-bearing nude mice. Our strategy may provide an effective solution for overcoming the heating effect and improving the PDT efficacy of upconversion nanoprobes, and has potential application in visualized theranostics of HER2-overexpressed breast cancer. Copyright © 2016 Elsevier Ltd. All rights reserved.

One-step nucleotide-programmed growth of porous upconversion nanoparticles: application to cell labeling and drug delivery

NASA Astrophysics Data System (ADS)

Zhou, Li; Li, Zhenhua; Liu, Zhen; Yin, Meili; Ren, Jinsong; Qu, Xiaogang

2014-01-01

A simple and ``green'' strategy has been reported for the first time to fabricate upconversion nanoparticles (UCNPs) by utilizing nucleotides as bio-templates. The influence of the functionalities present on the nucleotide on the production of nanoparticles was investigated in detail. Through the effects of nucleotides, the obtained nanoparticles possessed a porous structure. The use of the as-prepared UCNPs for cell imaging, drug delivery and versatile therapy applications were demonstrated. In view of the bright up-conversion luminescence as well as the excellent biocompatibility, and the good colloidal stability of the as-prepared UCNPs, we envision that our synthesis protocol might advance both the fields of UCNPs and biomolecule-based nanotechnology for future studies.A simple and ``green'' strategy has been reported for the first time to fabricate upconversion nanoparticles (UCNPs) by utilizing nucleotides as bio-templates. The influence of the functionalities present on the nucleotide on the production of nanoparticles was investigated in detail. Through the effects of nucleotides, the obtained nanoparticles possessed a porous structure. The use of the as-prepared UCNPs for cell imaging, drug delivery and versatile therapy applications were demonstrated. In view of the bright up-conversion luminescence as well as the excellent biocompatibility, and the good colloidal stability of the as-prepared UCNPs, we envision that our synthesis protocol might advance both the fields of UCNPs and biomolecule-based nanotechnology for future studies. Electronic supplementary information (ESI) available: Supporting figures. See DOI: 10.1039/c3nr04255c

Folic acid-functionalized up-conversion nanoparticles: toxicity studies in vivo and in vitro and targeted imaging applications

NASA Astrophysics Data System (ADS)

Sun, Lining; Wei, Zuwu; Chen, Haige; Liu, Jinliang; Guo, Jianjian; Cao, Ming; Wen, Tieqiao; Shi, Liyi

2014-07-01

Folate receptors (FRs) are overexpressed on a variety of human cancer cells and tissues, including cancers of the breast, ovaries, endometrium, and brain. This over-expression of FRs can be used to target folate-linked imaging specifically to FR-expressing tumors. Fluorescence is emerging as a powerful new modality for molecular imaging in both the diagnosis and treatment of disease. Combining innovative molecular biology and chemistry, we prepared three kinds of folate-targeted up-conversion nanoparticles as imaging agents (UCNC-FA: UCNC-Er-FA, UCNC-Tm-FA, and UCNC-Er,Tm-FA). In vivo and in vitro toxicity studies showed that these nanoparticles have both good biocompatibility and low toxicity. Moreover, the up-conversion luminescence imaging indicated that they have good targeting to HeLa cells and can therefore serve as potential fluorescent contrast agents.Folate receptors (FRs) are overexpressed on a variety of human cancer cells and tissues, including cancers of the breast, ovaries, endometrium, and brain. This over-expression of FRs can be used to target folate-linked imaging specifically to FR-expressing tumors. Fluorescence is emerging as a powerful new modality for molecular imaging in both the diagnosis and treatment of disease. Combining innovative molecular biology and chemistry, we prepared three kinds of folate-targeted up-conversion nanoparticles as imaging agents (UCNC-FA: UCNC-Er-FA, UCNC-Tm-FA, and UCNC-Er,Tm-FA). In vivo and in vitro toxicity studies showed that these nanoparticles have both good biocompatibility and low toxicity. Moreover, the up-conversion luminescence imaging indicated that they have good targeting to HeLa cells and can therefore serve as potential fluorescent contrast agents. Electronic supplementary information (ESI) available: Up-conversion luminescence spectra of UCNC-Er and UCNC-Er-FA, UCNC-Tm and UCNC-Tm-FA. Confocal luminescence imaging data collected as a series along the Z optical axis. See DOI: 10.1039/c4nr02312a

Infrared spectroscopy and upconversion luminescence behaviour of erbium doped yttrium (III) oxide phosphor

NASA Astrophysics Data System (ADS)

Dubey, Vikas; Tiwari, Ratnesh; Tamrakar, Raunak Kumar; Rathore, Gajendra Singh; Sharma, Chitrakant; Tiwari, Neha

2014-11-01

The paper reports upconversion luminescence behaviour and infra-red spectroscopic pattern of erbium doped yttrium (III) oxide phosphor. Sample was synthesized by solid state reaction method with variable concentration or erbium (0.5-2.5 mol%). The conventional solid state method is suitable for large scale production and eco-friendly method. The prepared sample was characterized by X-ray diffraction (XRD) technique. From structural analysis by XRD technique shows cubic structure of prepared sample with variable concentration of erbium and no impurity phase were found when increase the concentration of Er3+. Particle size was calculated by Scherer's formula and it varies from 67 nm to 120 nm. The surface morphology of prepared phosphor was determined by field emission gun scanning electron microscopy (FEGSEM) technique. The surface morphology of the sample shows good connectivity with grains as well as some agglomerates formation occurs in sample. The functional group analysis was done by Fourier transform infra-red technique (FTIR) analysis which confirm the formation of Y2O3:Er3+ phosphor was prepared. The results indicated that the Y2O3:Er3+ phosphors might have high upconversion efficiency because of their low vibrational energy. Under 980 nm laser excitation sample shows intense green emission at 555 nm and orange emission at 590 nm wavelength. For green emission transition occurs 2H11/2 → 4I15/2, 4S3/2 → 4I15/2 for upconversion emissions. Excited state absorption and energy transfer process were discussed as possible upconversion mechanisms. The near infrared luminescence spectra was recorded. The upconversion luminescence intensity increase with increasing the concentration or erbium up to 2 mol% after that luminescence intensity decreases due to concentration quenching occurs. Spectrophotometric determinations of peaks are evaluated by Commission Internationale de I'Eclairage (CIE) technique. From CIE technique the dominant peak of from PL spectra shows intense green emission so the prepared phosphor is may be useful for green light emitting diode (GLED) application.

High quantum-yield phosphors via quantum splitting and upconversion

NASA Astrophysics Data System (ADS)

Jeong, Joayoung

The Gd3+ ion has been used to induce quantum splitting in luminescent materials by using cross-relaxation energy transfer (CRET). In Nd:LiGdF4, quantum splitting results from a two-step CRET between Gd3+ and Nd3+, first involving a transition 6G→6I on Gd3+ and an excitation within the 4f3 configuration of Nd3+ followed by a second CRET that brings Gd3+ to 6P7/2. The excited Nd3+ ion rapidly relaxes nonradiatively to the emitting 4F3/2. The excited Gd3+ ion then transfers its energy back to Nd3+, which gives rise to the second photon. The result is a quantum yield of 1.05 +/- 0.35 with emission in the NIR following excitation at 175 nm. GdF3:Pr3+, Eu 3+ also exhibits quantum splitting, but only at very low concentration of Pr3+ (0.3%) and Eu3+ (0.2%), resulting in a quantum yield of approximately 20% under 160-nm excitation. Host intrinsic emission via a self-trapped exciton (STE) was also examined as a means to sensitize Gd3+ emission. The material ScPO4:Gd 3+ exhibits a high absolute quantum yield of 0.9 +/- 0.2 under 170-nm excitation, demonstrating a potentially new and efficient pathway for exciting quantum splitting phosphors. Single crystals of the material GdZrF7 were grown, and its structure was established via single-crystal X-ray diffraction methods. Doped samples of GdZrF7:Yb3+, Er3+ exhibit bright up-conversion luminescence with light output that is up to twice that of a commercial material based on the host Gd2O2S. When doped with Eu3+, the fluoride also emits a nearly white color under vacuum ultraviolet excitation with an absolute quantum yield near 0.9. The new compound Gd4.67(SiO4)3S was synthesized and studied. The structure was established via single-crystal X-ray methods, and the luminescence of Tb3+ samples was investigated.

Magnetic nanotubes

DOEpatents

Matsui, Hiroshi; Matsunaga, Tadashi

2010-11-16

A magnetic nanotube includes bacterial magnetic nanocrystals contacted onto a nanotube which absorbs the nanocrystals. The nanocrystals are contacted on at least one surface of the nanotube. A method of fabricating a magnetic nanotube includes synthesizing the bacterial magnetic nanocrystals, which have an outer layer of proteins. A nanotube provided is capable of absorbing the nanocrystals and contacting the nanotube with the nanocrystals. The nanotube is preferably a peptide bolaamphiphile. A nanotube solution and a nanocrystal solution including a buffer and a concentration of nanocrystals are mixed. The concentration of nanocrystals is optimized, resulting in a nanocrystal to nanotube ratio for which bacterial magnetic nanocrystals are immobilized on at least one surface of the nanotubes. The ratio controls whether the nanocrystals bind only to the interior or to the exterior surfaces of the nanotubes. Uses include cell manipulation and separation, biological assay, enzyme recovery, and biosensors.

The Sensitive Infrared Signal Detection by Sum Frequency Generation

NASA Technical Reports Server (NTRS)

Wong, Teh-Hwa; Yu, Jirong; Bai, Yingxin

2013-01-01

An up-conversion device that converts 2.05-micron light to 700 nm signal by sum frequency generation using a periodically poled lithium niobate crystal is demonstrated. The achieved 92% up-conversion efficiency paves the path to detect extremely weak 2.05-micron signal with well established silicon avalanche photodiode detector for sensitive lidar applications.

Snap-through twinkling energy generation through frequency up-conversion

NASA Astrophysics Data System (ADS)

Panigrahi, Smruti R.; Bernard, Brian P.; Feeny, Brian F.; Mann, Brian P.; Diaz, Alejandro R.

2017-07-01

A novel experimental energy harvester is investigated for its energy harvesting capability by frequency up-conversion using snap-through structures. In particular, a single-degree-of-freedom (SDOF) experimental energy harvester model is built using a snap-through nonlinear element. The snap-through dynamics is facilitated by the experimental setup of a twinkling energy generator (TEG) consisting of linear springs and attracting cylindrical bar magnets. A cylindrical coil of enamel-coated magnet wire is used as the energy generator. The governing equations are formulated mathematically and solved numerically for a direct comparison with the experimental results. The experimental TEG and the numerical simulation results show 25-fold frequency up-conversion and the power harvesting capacity of the SDOF TEG.

Thermal, optical and vibrational studies of tyrosine doped LaF3:Ce nanoparticles for bioimaging and biotagging

NASA Astrophysics Data System (ADS)

Singh, Amit T.

2018-05-01

Upconversion quantum dots of tyrosine doped LaF3:Ce nanoparticles have been synthesized by wet chemical route. The thermal studies (TGA/DTA) confirm the crystallinity and stability of different phases of synthesized nanoparticles. The UV-Visible spectra show multiple absorption edges at 215.60 nm and 243.10 nm indicating quantum dot nature of the synthesized nanoparticles. The PL spectra showed upconversion with sharp emission peak at 615 nm (red colour). The FT-RAMAN spectra of the synthesized nanoparticles show the modification of the surface of the nanoparticles in the form of functional groups and skeletal groups. Upconversion nature of the synthesized nanoparticles indicates their potential application in bioimaging and biotagging.

Bi-stable frequency up-conversion piezoelectric energy harvester driven by non-contact magnetic repulsion

NASA Astrophysics Data System (ADS)

Tang, Q. C.; Yang, Y. L.; Li, Xinxin

2011-12-01

This paper presents miniaturized energy harvesters, where the frequency up-conversion technique is used to improve the bandwidth of vibration energy harvesters. The proposed and developed miniature piezoelectric energy harvester utilizes magnetic repulsion forces to achieve non-contact frequency up-conversion, thereby avoiding mechanical collision and wear for long-term working durability. A pair of piezoelectric resonant cantilevers is micro-fabricated to generate electric power. A simplified model involving linear oscillators and magnetic interaction is deployed to demonstrate the feasibility of the device design. A bench-top harvester has been fabricated and characterized, resulting in average power generation of over 10 µW within a broad frequency range of 10-22 Hz under 1g acceleration.

Nanoparticle-based luminescent probes for intracellular sensing and imaging of pH.

PubMed

Schäferling, Michael

2016-05-01

Fluorescence imaging microscopy is an essential tool in biomedical research. Meanwhile, various fluorescent probes are available for the staining of cells, cell membranes, and organelles. Though, to monitor intracellular processes and dysfunctions, probes that respond to ubiquitous chemical parameters determining the cellular function such as pH, pO2 , and Ca(2+) are required. This review is focused on the progress in the design, fabrication, and application of photoluminescent nanoprobes for sensing and imaging of pH in living cells. The advantages of using nanoprobes carrying fluorescent pH indicators compared to single molecule probes are discussed as well as their limitations due to the mostly lysosomal uptake by cells. Particular attention is paid to ratiometric dual wavelength nanosensors that enable intrinsic referenced measurements. Referencing and proper calibration procedures are basic prerequisites to carry out reliable quantitative pH determinations in complex samples such as living cells. A variety of examples will be presented that highlight the diverseness of nanocarrier materials (polymers, micelles, silica, quantum dots, carbon dots, gold, photon upconversion nanocrystals, or bacteriophages), fluorescent pH indicators for the weak acidic range, and referenced sensing mechanisms, that have been applied intracellularly up to now. WIREs Nanomed Nanobiotechnol 2016, 8:378-413. doi: 10.1002/wnan.1366 For further resources related to this article, please visit the WIREs website. © 2015 Wiley Periodicals, Inc.

Multifunctional hydroxyapatite/Na(Y/Gd)F4:Yb3+,Er3+ composite fibers for drug delivery and dual modal imaging.

PubMed

Liu, Min; Liu, Hui; Sun, Shufen; Li, Xuejiao; Zhou, Yanmin; Hou, Zhiyao; Lin, Jun

2014-02-04

Porous hydroxyapatite (HAp) composite fibers functionalized with up-conversion (UC) luminescent and magnetic Na(Y/Gd)F4:Yb(3+),Er(3+) nanocrystals (NCs) have been fabricated via electrospinning. After transferring hydrophobic oleic acid-capped Na(Y/Gd)F4:Yb(3+),Er(3+) NCs into aqueous solution, these water-dispersible NCs were dispersed into precursor electrospun solution containing CTAB. Na(Y/Gd)F4:Yb(3+),Er(3+)@HAp composite fibers were fabricated by the high temperature treatment of the electrospun Na(Y/Gd)F4:Yb(3+),Er(3+) NCs decorated precursor fibers. The biocompatibility test on MC 3T3-E1 cells using MTT assay shows that the HAp composite fibers have negligible cytotoxity, which reveals the HAp composite fibers could be a drug carrier for drug delivery. Because the contrast brightening is enhanced at increased concentrations of Gd(3+), the HAp composite fibers can serve as T1 magnetic resonance imaging contrast agents. In addition, the composites uptaken by MC 3T3-E1 cells present the UC luminescent emission of Er(3+) under the excitation of a 980 nm near-infrared laser. The above findings reveal Na(Y/Gd)F4:Yb(3+),Er(3+)@HAp composite fibers have potential applications in drug storage/release and magnetic resonance/UC luminescence imaging.

Dye-Sensitized Core/Active Shell Upconversion Nanoparticles for Optogenetics and Bioimaging Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Xiang; Zhang, Yuanwei; Takle, Kendra

2016-01-26

Near Infrared (NIR) dye-sensitized upconversion nanoparticles (UCNPs) have recently been proposed in order to broaden the absorption range and to boost upconversion efficiency. However, implementing this strategy has been limited only to bare core UCNP structures that are faintly luminescent. Herein, we report on an approach to achieve significantly enhanced upconversion luminescence in dye-sensitized core-active shell UCNPs with a broadened absorption range via the doping of ytterbium ions in the UCNP shell in order to bridge the energy transfer from the dye to the UCNP core. As a result, we have been able to synergize the two most practical upconversionmore » booster effectors (dye-sensitizing and core/shell enhancement). The absolute quantum yield of our dye-sensitized core/active shell UCNPs at 800 nm was determined to be ~6% at 2 W/cm2, about 33 times larger than the highest value reported to date for existing 800 nm excitable UCNPs. Moreover, for the first time, by using dye-sensitized core/active shell UCNP embedded poly(methyl methacrylate) polymer implantable systems, we successfully shifted the optogenetic neuron excitation window to a wavelength that is compatible with deep tissue penetrable near the infrared wavelength at 800 nm. Finally, amphiphilic triblock copolymer, Pluronic F127 coatings permit the transfer of hydrophobic UCNPs into water, resulting in water-soluble nanoparticles with well-preserved optical property in aqueous solution. We believe that this research offers a new solution to enhance upconversion efficiency for photonic and biophotonic purposes and opens up new opportunities to use UCNPs as a NIR relay for optogenetic applications.« less

Tetherless near-infrared control of brain activity in behaving animals using fully implantable upconversion microdevices.

PubMed

Wang, Ying; Lin, Xudong; Chen, Xi; Chen, Xian; Xu, Zhen; Zhang, Wenchong; Liao, Qinghai; Duan, Xin; Wang, Xin; Liu, Ming; Wang, Feng; He, Jufang; Shi, Peng

2017-10-01

Many nanomaterials can be used as sensors or transducers in biomedical research and they form the essential components of transformative novel biotechnologies. In this study, we present an all-optical method for tetherless remote control of neural activity using fully implantable micro-devices based on upconversion technology. Upconversion nanoparticles (UCNPs) were used as transducers to convert near-infrared (NIR) energy to visible light in order to stimulate neurons expressing different opsin proteins. In our setup, UCNPs were packaged in a glass micro-optrode to form an implantable device with superb long-term biocompatibility. We showed that remotely applied NIR illumination is able to reliably trigger spiking activity in rat brains. In combination with a robotic laser projection system, the upconversion-based tetherless neural stimulation technique was implemented to modulate brain activity in various regions, including the striatum, ventral tegmental area, and visual cortex. Using this system, we were able to achieve behavioral conditioning in freely moving animals. Notably, our microscale device was at least one order of magnitude smaller in size (∼100 μm in diameter) and two orders of magnitude lighter in weight (less than 1 mg) than existing wireless optogenetic devices based on light-emitting diodes. This feature allows simultaneous implantation of multiple UCNP-optrodes to achieve modulation of brain function to control complex animal behavior. We believe that this technology not only represents a novel practical application of upconversion nanomaterials, but also opens up new possibilities for remote control of neural activity in the brains of behaving animals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Light-Emitting Photon-Upconversion Nanoparticles in the Generation of Transdermal Reactive-Oxygen Species.

PubMed

Prieto, Martin; Rwei, Alina Y; Alejo, Teresa; Wei, Tuo; Lopez-Franco, Maria Teresa; Mendoza, Gracia; Sebastian, Victor; Kohane, Daniel S; Arruebo, Manuel

2017-12-06

Common photosensitizers used in photodynamic therapy do not penetrate the skin effectively. In addition, the visible blue and red lights used to excite such photosensitizers have shallow penetration depths through tissue. To overcome these limitations, we have synthesized ultraviolet- and visible-light-emitting, energy-transfer-based upconversion nanoparticles and coencapsulated them inside PLGA-PEG (methoxy poly(ethylene glycol)-b-poly(lactic-co-glycolic acid)) nanoparticles with the photosensitizer protoporphyrin IX. Nd 3+ has been introduced as a sensitizer in the upconversion nanostructure to allow its excitation at 808 nm. The subcytotoxic doses of the hybrid nanoparticles have been evaluated on different cell lines (i.e., fibroblasts, HaCaT, THP-1 monocytic cell line, U251MG (glioblastoma cell line), and mMSCs (murine mesenchymal stem cells). Upon NIR (near infrared)-light excitation, the upconversion nanoparticles emitted UV and VIS light, which consequently activated the generation of reactive-oxygen species (ROS). In addition, after irradiating at 808 nm, the resulting hybrid nanoparticles containing both upconversion nanoparticles and protoporphyrin IX generated 3.4 times more ROS than PLGA-PEG nanoparticles containing just the same dose of protoporphyrin IX. Their photodynamic effect was also assayed on different cell cultures, demonstrating their efficacy in selectively killing treated and irradiated cells. Compared to the topical application of the free photosensitizer, enhanced skin permeation and penetration were observed for the nanoparticulate formulation, using an ex vivo human-skin-permeation experiment. Whereas free protoporphyrin IX remained located at the outer layer of the skin, nanoparticle-encapsulated protoporphyrin IX was able to penetrate through the epidermal layer slightly into the dermis.

Ferroelectric polymer-ceramic composite thick films for energy storage applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Paritosh; Borkar, Hitesh; Singh, B. P.

2014-08-15

We have successfully fabricated large area free standing polyvinylidene fluoride -Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} (PVDF-PZT) ferroelectric polymer-ceramic composite (wt% 80–20, respectively) thick films with an average diameter (d) ∼0.1 meter and thickness (t) ∼50 μm. Inclusion of PZT in PVDF matrix significantly enhanced dielectric constant (from 10 to 25 at 5 kHz) and energy storage capacity (from 11 to 14 J/cm{sup 3}, using polarization loops), respectively, and almost similar leakage current and mechanical strength. Microstructural analysis revealed the presence of α and β crystalline phases and homogeneous distribution of PZT crystals in PVDF matrix. It was also found that apartmore » from the microcrystals, well defined naturally developed PZT nanocrystals were embedded in PVDF matrix. The observed energy density indicates immense potential in PVDF-PZT composites for possible applications as green energy and power density electronic elements.« less

Smart pH-responsive upconversion nanoparticles for enhanced tumor cellular internalization and near-infrared light-triggered photodynamic therapy.

PubMed

Wang, Sheng; Zhang, Lei; Dong, Chunhong; Su, Lin; Wang, Hanjie; Chang, Jin

2015-01-01

A smart pH-responsive photodynamic therapy system based on upconversion nanoparticle loaded PEG coated polymeric lipid vesicles (RB-UPPLVs) was designed and prepared. These RB-UPPLVs which are promising agents for deep cancer photodynamic therapy applications can achieve enhanced tumor cellular internalization and near-infrared light-triggered photodynamic therapy.

Up-Conversion Y2O3:Yb(3+),Er(3+) Hollow Spherical Drug Carrier with Improved Degradability for Cancer Treatment.

PubMed

Ge, Kun; Zhang, Cuimiao; Sun, Wentong; Liu, Huifang; Jin, Yi; Li, Zhenhua; Liang, Xing-Jie; Jia, Guang; Zhang, Jinchao

2016-09-28

The rare earth hollow spheres with up-conversion luminescence properties have shown potential applications in drug delivery and bioimaging fields. However, there have been few reports for the degradation properties of rare earth oxide drug carriers. Herein, uniform and well-dispersed Y2O3:Yb(3+),Er(3+) hollow spheres (YOHSs) have been fabricated by a general Pechini sol-gel process with melamine formaldehyde colloidal spheres as template. The novel YOHSs with up-conversion luminescence has good drug loading amount and drug-release efficiency; moreover, it exhibits pH-responsive release patterns. In particular, the YOHSs sample exhibits low cytotoxicity and excellent degradable properties in acid buffer. After the sample was loaded with anticancer drug doxorubicin (DOX), the antitumor result in vitro indicates that YOHS-DOX might be effective in cancer treatment. The animal imaging test also reveals that the YOHSs drug carrier can be used as an outstanding luminescent probe for bioimaging in vivo application prospects. The results suggest that the degradable drug carrier with up-conversion luminescence may enhance the delivery efficiency of drugs and improve the cancer therapy in clinical applications.

Structural morphology, upconversion luminescence and optical thermometric sensing behavior of Y2O3:Er(3+)/Yb(3+) nano-crystalline phosphor.

PubMed

Joshi, C; Dwivedi, A; Rai, S B

2014-08-14

Infrared-to-visible upconverting rare earths Er(3+)/Yb(3+) co-doped Y2O3 nano-crystalline phosphor samples have been prepared by solution combustion method followed by post-heat treatment at higher temperatures. A slight increase in average crystallite size has been found on calcinations verified by X-ray analysis. Transmission electron microscopy (TEM) confirms the nano-crystalline nature of the as-prepared and calcinated samples. Fourier transform infrared (FTIR) analysis shows the structural changes in as-prepared and calcinated samples. Upconversion and downconversion emission recorded using 976 and 532 nm laser sources clearly demonstrates a better luminescence properties in the calcinated samples as compared to as-prepared sample. Upconversion emission has been quantified in terms of standard chromaticity diagram (CIE) showing a shift in overall upconversion emission of as-prepared and calcinated samples. Temperature sensing behaviour of this material has also been investigated by measurement of fluorescence intensity ratio (FIR) of various signals in green emission in the temperature range of 315 to 555 K under 976 nm laser excitation. Copyright © 2014 Elsevier B.V. All rights reserved.

Fabrication and evaluation of chitosan/NaYF4:Yb3+/Tm3+ upconversion nanoparticles composite beads based on the gelling of Pickering emulsion droplets.

PubMed

Yan, Huiqiong; Chen, Xiuqiong; Shi, Jia; Shi, Zaifeng; Sun, Wei; Lin, Qiang; Wang, Xianghui; Dai, Zihao

2017-02-01

The rare earth ion doped upconversion nanoparticles (UCNPs) synthesized by hydrophobic organic ligands possess poor solubility and low fluorescence quantum yield in aqueous media. To conquer this issue, NaYF 4 :Yb 3+ /Tm 3+ UCNPs, synthesized by a hydrothermal method, were coated with F127 and then assembled with chitosan to fabricate the chitosan/NaYF 4 :Yb 3+ /Tm 3+ composite beads (CS/NaYF 4 :Yb 3+ /Tm 3+ CBs) by Pickering emulsion system. The characterization results revealed that the as-synthesized NaYF 4 :Yb 3+ /Tm 3+ UCNPs with an average size of 20nm exhibited spherical morphology, high crystallinity and characteristic emission upconversion fluorescence with an overall blue color output. The NaYF 4 :Yb 3+ /Tm 3+ UCNPs were successfully conjugated on the surface of chitosan beads by the gelling of emulsion droplets. The resultant CS/NaYF 4 :Yb 3+ /Tm 3+ CBs showed good upconversion luminescent property, drug-loading capacity, release performance and excellent biocompatibility, exhibiting great potentials in targeted drug delivery and tissue engineering with potential tracking capability and lasting release performance. Copyright © 2016 Elsevier B.V. All rights reserved.

NIR Ratiometric Luminescence Detection of pH Fluctuation in Living Cells with Hemicyanine Derivative-Assembled Upconversion Nanophosphors.

PubMed

Li, Haixia; Dong, Hao; Yu, Mingming; Liu, Chunxia; Li, Zhanxian; Wei, Liuhe; Sun, Ling-Dong; Zhang, Hongyan

2017-09-05

It is crucial for cell physiology to keep the homeostasis of pH, and it is highly demanded yet challenging to develop luminescence resonance energy transfer (LRET)-based near-infrared (NIR) ratiometric luminescent sensor for the detection of pH fluctuation with NIR excitation. As promising energy donors for LRET, upconversion nanoparticles (UCNPs) have been widely used to fabricate nanosensors, but the relatively low LRET efficiency limits their application in bioassay. To improve the LRET efficiency, core/shell/shell structured β-NaGdF 4 @NaYF 4 :Yb,Tm@NaYF 4 UCNPs were prepared and decorated with hemicyanine dyes as an LRET-based NIR ratiometric luminescent pH fluctuation-nanosensor for the first time. The as-developed nanosensor not only exhibits good antidisturbance ability, but it also can reversibly sense pH and linearly sense pH in a range of 6.0-9.0 and 6.8-9.0 from absorption and upconversion emission spectra, respectively. In addition, the nanosensor displays low dark toxicity under physiological temperature, indicating good biocompatibility. Furthermore, live cell imaging results revealed that the sensor can selectively monitor pH fluctuation via ratiometric upconversion luminescence behavior.

DNA-assisted upconversion nanoplatform for imaging-guided synergistic therapy and laser-switchable drug detoxification.

PubMed

Li, Luoyuan; Hao, Panlong; Wei, Peng; Fu, Limin; Ai, Xicheng; Zhang, Jianping; Zhou, Jing

2017-08-01

The side effects of chemotherapy bring significant physical and psychological suffering to patients. To solve this urgent medical problem, Yb 3+ and Er 3+ co-doped NaLuF 4 upconversion nanoparticles (UCNPs) were constructed for upconversion luminescence (UCL)-labeled diagnosis under 980 nm laser irradiation. The UCNPs were then modified layer by layer with polypyrrole and a special programming DNA segment as photothermal conversion agents and controllable drug carriers, respectively. The nanoplatform was successfully used for imaging-guided synergistic therapy (photothermal therapy and chemotherapy) at a safe power density (300 mW cm -2 ), and DNA-assisted detoxification at lower temperature in cancer cells when the laser off. The synergistic therapy of the nanoplatform achieved a higher therapeutic index (∼85%) than chemotherapy only (∼44%) and photothermal therapy only (∼25%) in vitro. In vivo experiments also suggested that the nanoplatform had a higher therapeutic effect and lower side effects. The toxicity study was also evaluated, indicating the nanoplatform is low toxic to living system. This multifunctional upconversion nanoplatform provided an innovative method for imaging-guided photothermal-chemotherapy and laser-switchable drug detoxification. Copyright © 2017 Elsevier Ltd. All rights reserved.

Excitonic luminescence upconversion in a two-dimensional semiconductor

DOE PAGES

Jones, Aaron M.; Yu, Hongyi; Schaibley, John R.; ...

2015-12-21

Photon upconversion is an elementary light-matter interaction process in which an absorbed photon is re-emitted at higher frequency after extracting energy from the medium. Furthermore, this phenomenon lies at the heart of optical refrigeration in solids(1), where upconversion relies on anti-Stokes processes enabled either by rare-earth impurities(2) or exciton-phonon coupling(3). We demonstrate a luminescence upconversion process from a negatively charged exciton to a neutral exciton resonance in monolayer WSe2, producing spontaneous anti-Stokes emission with an energy gain of 30 meV. Polarization-resolved measurements find this process to be valley selective, unique to monolayer semiconductors(4). Since the charged exciton binding energy(5) closelymore » matches the 31 meV A(1)' optical phonon(6-9), we ascribe the spontaneous excitonic anti-Stokes to doubly resonant Raman scattering, where the incident and outgoing photons are in resonance with the charged and neutral excitons, respectively. Additionally, we resolve a charged exciton doublet with a 7 meV splitting, probably induced by exchange interactions, and show that anti-Stokes scattering is efficient only when exciting the doublet peak resonant with the phonon, further confirming the excitonic doubly resonant picture.« less

A highly sensitive biosensing platform based on upconversion nanoparticles and graphene quantum dots for the detection of Ag+

NASA Astrophysics Data System (ADS)

He, Lu; Yang, Lin; Zhu, Hao; Dong, Wenkui; Ding, Yujie; Zhu, Jun-Jie

2017-06-01

A novel luminescence ‘Turn-On’ nanoplatform for the sensitive sensing of Ag+ was fabricated based on luminescence resonance energy transfer technique between sodium citrate functionalized upconversion nanoparticles (Cit-UCNPs, energy donor) and graphene quantum dots (GQDs, energy acceptor). Amino-labeled single-stranded DNA (NH2-ssDNA) containing a number of cytosine (C) was conjugated on the surface of the Cit-UCNPs to capture Ag+ ions. Due to the π-π stacking interaction between NH2-ssDNA and GQDs, the upconversion luminescence can be quenched. However, upon the addition of Ag+, the π-π stacking interaction weakens due to the formation of the hairpin structure of C-Ag+-C on the UCNPs. As a result, GQDs will leave the surface of the UCNPs and the upconversion luminescence can be enhanced (Turn-On). Based on this fact, the sensor was developed for the detection of Ag+ with a linear concentration range from 2 × 10-4 to 1 μM and a detection limit as low as 60 pM. The assay method is fairly simple with high selectivity and sensitivity, which can be used for the determination of Ag+ in environmental water samples.

Solar upconversion with plasmon-enhanced bimolecular complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dionne, Jennifer

2017-04-14

Upconversion of sub-bandgap photons is a promising approach to exceed the Shockley-Queisser limit in solar technologies. However, due to the low quantum efficiencies and narrow absorption bandwidths of upconverters, existing systems have only led to fractional percent improvements in photovoltaic devices (~0.01%). In this project, we aimed to develop an efficient upconverting material that could improve cell efficiencies by at least one absolute percent. To achieve this goal, we first used thermodynamic calculations to determine cell efficiencies with realistic upconverting materials. Then, we designed, synthesized, and characterized nanoantennas that promise >100x enhancement in both the upconverter absorption cross-section and emissivemore » radiative rate. Concurrently, we optimized the upconverer by designing new ionic and molecular complexes that promise efficient solid-state upconversion. Lastly, with Bosch, we simulated record-efficiency semi-transparent cells that will allow for ready incorporation of our upconverting materials. While we were not successful in designing record efficiency upconverters during our three years of funding, we gained significant insight into the existing limitations of upconverters and how to best address these challenges. Ongoing work is aimed at addressing these limitations, to make upconversion a cost-competitive solar technology in future years.« less

Ultrasmall lanthanide-doped nanoparticles as multimodal platforms

NASA Astrophysics Data System (ADS)

Yust, Brian G.; Pedraza, Francisco J.; Sardar, Dhiraj K.

2014-03-01

Recently, there has been a great amount of interest in nanoparticles which are able to provide a platform with high contrast for multiple imaging modalities in order to advance the tools available to biomedical researchers and physicians. However, many nanoparticles do not have ideal properties to provide high contrast in different imaging modes. In order to address this, ultrasmall lanthanide doped oxide and fluoride nanoparticles with strong NIR to NIR upconversion fluorescence and a strong magnetic response for magnetic resonance imaging (MRI) have been developed. Specifically, these nanoparticles incorporate gadolinium, dysprosium, or a combination of both into the nano-crystalline host to achieve the magnetic properties. Thulium, erbium, and neodymium codopants provide the strong NIR absorption and emission lines that allow for deeper tissue imaging since near infrared light is not strongly absorbed or scattered by most tissues within this region. This also leads to better image quality and lower necessary excitation intensities. As a part of the one pot synthesis, these nanoparticles are coated with peg, pmao, or d-glucuronic acid to make them water soluble, biocompatible, and bioconjugable due to the available carboxyl or amine groups. Here, the synthesis, morphological characterization, magnetic response, NIR emission, and the quantum yield will be discussed. Cytotoxicity tested through cell viability at varying concentrations of nanoparticles in growth media will also be discussed.

Spectroscopy and excitation dynamics of the trivalent lanthanides Tm(3+) and Ho(3+) in LiYF4

NASA Technical Reports Server (NTRS)

Walsh, Brian M.

1995-01-01

A detailed study of the spectroscopy and excitation dynamics Tm3+ and Ho3+ in yttrium lithium fluoride, LiYF4 (YLF), has been done. Absorption spectroscopy is utilized in the Judd-Ofelt theory to determine radiative transition rates of spontaneous emission. Luminescence spectroscopy is studied under cw diode laser excitation at 785nm. The effect of dopant ion concentration and excitation power on the observed luminescence are considered in these measurements. An analysis of these measurements have been used to determine channels of energy transfer between Tm3+ and Ho3+ ions. The temporal response of Tm and Ho in singly and co-doped YLF to pulsed laser excitation with a Ti:Al2O3 laser and a CoMgF2 laser turned to various wavelengths have also been studied. The energy transfer mechanisms of cross relaxation, upconversion, and resonant energy transfer between Tm3+ and Ho3+ ions have been modeled, and the model parameters extracted by a fitting procedure to the measured temporal response curves. Rate equation approaches to modeling are presented that result in predictions of rate constants for energy transfer processes, as well as more conventional approaches to modeling such as the Forster-Dexter models, which give the interaction strengths in terms of microscopic interaction parameters.

Tunable upconversion luminescence of monodisperse Y2O3: Er3+/Yb3+/Tm3+ nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Qibai; Lin, Shaoteng; Xie, Zhongxiang; Zhang, Liqing; Qian, Yannan; Wang, Yaodong; Zhang, Haiyan

2017-12-01

Monodisperse Y2O3: Er3+/Yb3+/Tm3+ nanoparticles with various dopant concentrations have been synthesized successfully by a homogeneous precipitation method. Their phase structures and surface morphologies have been characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The diversities of upconversion luminescence spectra and CIE coordinates of prepared samples are investigated in detail at room temperature under 980 nm excitation. Through adjusting the concentrations of Yb3+, Tm3+ and Er3+ ions, three upconversion emission bands in red, green and blue region could be tunable to achieve the color of interest and near white light emission can be obtained in the tri-doped Y2O3 nanoparticles for a variety of application.

Surface chemical modification of nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Helms, Brett Anthony; Milliron, Delia Jane; Rosen, Evelyn Louise

Nanocrystals comprising organic ligands at surfaces of the plurality of nanocrystals are provided. The organic ligands are removed from the surfaces of the nanocrystals using a solution comprising a trialkyloxonium salt in a polar aprotic solvent. The removal of the organic ligands causes the nanocrystals to become naked nanocrystals with cationic surfaces.

A cobalt oxyhydroxide-modified upconversion nanosystem for sensitive fluorescence sensing of ascorbic acid in human plasma

NASA Astrophysics Data System (ADS)

Cen, Yao; Tang, Jun; Kong, Xiang-Juan; Wu, Shuang; Yuan, Jing; Yu, Ru-Qin; Chu, Xia

2015-08-01

Ascorbic acid (AA), a potent antioxidant readily scavenging reactive species, is a crucial micronutrient involved in many biochemical processes. Here, we have developed a cobalt oxyhydroxide (CoOOH)-modified upconversion nanosystem for fluorescence sensing of AA activity in human plasma. The nanosystem consists of upconversion nanoparticles (UCNPs) NaYF4:30% Yb,0.5% Tm@NaYF4, which serve as energy donors, and CoOOH nanoflakes formed on the surface of UCNPs, which act as efficient energy acceptors. The fluorescence resonance energy transfer (FRET) process from the UCNPs to the absorbance of the CoOOH nanoflakes occurs in the nanosystem. The AA-mediated specific redox reaction reduces CoOOH into Co2+, leading to the inhibition of FRET, and resulting in the recovery of upconversion emission spectra. On the basis of these features, the nanosystem can be used for sensing AA activity with sensitivity and selectivity. Moreover, due to the minimizing background interference provided by UCNPs, the nanosystem has been applied to monitoring AA levels in human plasma sample with satisfactory results. The proposed approach may potentially provide an analytical platform for research and clinical diagnosis of AA related diseases.Ascorbic acid (AA), a potent antioxidant readily scavenging reactive species, is a crucial micronutrient involved in many biochemical processes. Here, we have developed a cobalt oxyhydroxide (CoOOH)-modified upconversion nanosystem for fluorescence sensing of AA activity in human plasma. The nanosystem consists of upconversion nanoparticles (UCNPs) NaYF4:30% Yb,0.5% Tm@NaYF4, which serve as energy donors, and CoOOH nanoflakes formed on the surface of UCNPs, which act as efficient energy acceptors. The fluorescence resonance energy transfer (FRET) process from the UCNPs to the absorbance of the CoOOH nanoflakes occurs in the nanosystem. The AA-mediated specific redox reaction reduces CoOOH into Co2+, leading to the inhibition of FRET, and resulting in the recovery of upconversion emission spectra. On the basis of these features, the nanosystem can be used for sensing AA activity with sensitivity and selectivity. Moreover, due to the minimizing background interference provided by UCNPs, the nanosystem has been applied to monitoring AA levels in human plasma sample with satisfactory results. The proposed approach may potentially provide an analytical platform for research and clinical diagnosis of AA related diseases. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03588k

Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOEpatents

Weiss, Shimon [Pinole, CA; Bruchez, Jr., Marcel; Alivisatos, Paul [Oakland, CA

2008-01-01

A semiconductor nanocrystal compound is described capable of linking to an affinity molecule. The compound comprises (1) a semiconductor nanocrystal capable of emitting electromagnetic radiation and/or absorbing energy, and/or scattering or diffracting electromagnetic radiation--when excited by an electromagnetic radiation source or a particle beam; and (2) an affinity molecule linked to the semiconductor nanocrystal. The semiconductor nanocrystal is linked to an affinity molecule to form a semiconductor nanocrystal probe capable of bonding with a detectable substance. Exposure of the semiconductor nanocrystal to excitation energy will excite the semiconductor nanocrystal causing the emission of electromagnetic radiation. Further described are processes for respectively: making the luminescent semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and using the probe to determine the presence of a detectable substance in a material.

Noscapinoids bearing silver nanocrystals augmented drug delivery, cytotoxicity, apoptosis and cellular uptake in B16F1, mouse melanoma skin cancer cells.

PubMed

Soni, Naina; Jyoti, Kiran; Jain, Upendra Kumar; Katyal, Anju; Chandra, Ramesh; Madan, Jitender

2017-06-01

Noscapine (Nos) and reduced brominated analogue of noscapine (Red-Br-Nos) prevent cellular proliferation and induce apoptosis in cancer cells either alone or in combination with other chemotherapeutic drugs. However, owing to poor physicochemical properties, Nos and Red-Br-Nos have demonstrated their anticancer activity at higher and multiple doses. Therefore, in present investigation, silver nanocrystals of noscapinoids (Nos-Ag 2+ nanocrystals and Red-Br-Nos-Ag 2+ nanocrystals) were customized to augment drug delivery, cytotoxicity, apoptosis and cellular uptake in B16F1 mouse melanoma cancer cells. Nos-Ag 2+ nanocrystals and Red-Br-Nos-Ag 2+ nanocrystals were prepared separately by precipitation method. The mean particle size of Nos-Ag 2+ nanocrystals was measured to be 25.33±3.52nm, insignificantly (P>0.05) different from 27.43±4.51nm of Red-Br-Nos-Ag 2+ nanocrystals. Furthermore, zeta-potential of Nos-Ag 2+ nanocrystals was determined to be -25.3±3.11mV significantly (P<0.05) different from -15.2±3.33mV of Red-Br-Nos-Ag 2+ nanocrystals. The shape of tailored nanocrystals was slightly spherical and or irregular in shape. The architecture of Nos-Ag 2+ nanocrystals and Red-Br-Nos-Ag 2+ nanocrystals was crystalline in nature. FT-IR spectroscopy evinced the successful interaction of Ag 2+ nanocrystals with Nos and Red-Br-Nos, respectively. The superior therapeutic efficacy of tailored nanocrystals was measured in terms of enhanced cytotoxicity, apoptosis and cellular uptake. The Nos-Ag 2+ nanocrystals and Red-Br-Nos-Ag 2+ nanocrystals exhibited an IC 50 of 16.6μM and 6.5μM, significantly (P<0.05) lower than 38.5μM of Nos and 10.3μM of Red-Br-Nos, respectively. Finally, cellular morphological alterations in B16F1 cells upon internalization of Nos-Ag 2+ nanocrystals and Red-Br-Nos-Ag 2+ nanocrystals provided the evidences for accumulation within membrane-bound cytoplasmic vacuoles and in enlarged lysosomes and thus triggered mitochondria mediated apoptosis via caspase activation. Preliminary investigations substantiated that Nos-Ag 2+ nanocrystals and Red-Br-Nos-Ag 2+ nanocrystals must be further explored and utilized for the delivery of noscapinoids to melanoma cancer cells. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Silicon nanocrystal inks, films, and methods

DOEpatents

Wheeler, Lance Michael; Kortshagen, Uwe Richard

2015-09-01

Silicon nanocrystal inks and films, and methods of making and using silicon nanocrystal inks and films, are disclosed herein. In certain embodiments the nanocrystal inks and films include halide-terminated (e.g., chloride-terminated) and/or halide and hydrogen-terminated nanocrystals of silicon or alloys thereof. Silicon nanocrystal inks and films can be used, for example, to prepare semiconductor devices.

An external template-free route to uniform semiconducting hollow mesospheres and their use in photocatalysis

NASA Astrophysics Data System (ADS)

Yang, Di; Wang, Mengye; Zou, Bin; Zhang, Gu Ling; Lin, Zhiqun

2015-07-01

Solid amorphous TiO2 mesospheres were synthesized by controlled hydrolysis of Ti-containing precursors. Subsequently, solid TiO2 mesospheres were exploited as scaffolds and subjected to a one-step external template-free hydrothermal treatment, yielding intriguing hollow anatase TiO2 mesospheres. The synthetic protocol was optimized by investigating the effect of buffer reagents and fluoride ions on the formation of hollow TiO2 spheres. The diameter of hollow mesospheres, ranging from 308 to 760 nm, can be readily tailored by varying the precursor concentration. The average thickness of a shell composed of TiO2 nanocrystals was approximately 40 nm with a mean crystal size of 12.4-20.0 nm. Such hollow TiO2 mesospheres possessed a large surface area and were employed in photocatalytic degradation of methylene blue under UV irradiation. Interestingly, the synthetic conditions were found to exert a significant influence on the photocatalytic ability of hollow TiO2 mesospheres. The correlation between the degradation ability of hollow TiO2 mesospheres and the precursor concentration as well as the hydrothermal time was scrutinized. The optimal photocatalytic performance of hollow TiO2 mesospheres was identified.Solid amorphous TiO2 mesospheres were synthesized by controlled hydrolysis of Ti-containing precursors. Subsequently, solid TiO2 mesospheres were exploited as scaffolds and subjected to a one-step external template-free hydrothermal treatment, yielding intriguing hollow anatase TiO2 mesospheres. The synthetic protocol was optimized by investigating the effect of buffer reagents and fluoride ions on the formation of hollow TiO2 spheres. The diameter of hollow mesospheres, ranging from 308 to 760 nm, can be readily tailored by varying the precursor concentration. The average thickness of a shell composed of TiO2 nanocrystals was approximately 40 nm with a mean crystal size of 12.4-20.0 nm. Such hollow TiO2 mesospheres possessed a large surface area and were employed in photocatalytic degradation of methylene blue under UV irradiation. Interestingly, the synthetic conditions were found to exert a significant influence on the photocatalytic ability of hollow TiO2 mesospheres. The correlation between the degradation ability of hollow TiO2 mesospheres and the precursor concentration as well as the hydrothermal time was scrutinized. The optimal photocatalytic performance of hollow TiO2 mesospheres was identified. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02685g

Luminescence studies and infrared emission of erbium-doped calcium zirconate phosphor.

PubMed

Tiwari, Neha; Dubey, Vikas

2016-05-01

The near-infrared-to-visible upconversion luminescence behaviour of Er(3+)-doped CaZrO3 phosphor is discussed in this manuscript. The phosphor was prepared by a combustion synthesis technique that is suitable for less-time-taking techniques for nanophosphors. The starting materials used for sample preparation were Ca(NO3)2.4H2O, Zr(NO3)4 and Er(NO3)2, and urea was used as a fuel. The prepared sample was characterized by X-ray diffraction (XRD). The surface morphology of prepared phosphor was determined by field emission gun scanning electron microscopy (FEGSEM). The functional group analysis was determined by Fourier transform infrared (FTIR) spectroscopy. All prepared phosphors with variable Er(3+) concentrations (0.5-2.5 mol%) were studied by photoluminescence analysis. It was found that the excitation spectra of the prepared phosphor showed a sharp excitation peak centred at 980 nm. The emission spectra with variable Er(3+) concentrations showed strong peaks in the 555 nm and 567 nm range, with a dominant peak at 555 nm due to the ((2)H(11/2),(4)S(3/2)) transition and a weaker transition at 567 nm associated with 527 nm. Spectrophotometric determination of the peak was evaluated by the Commission Internationale de I'Eclairage (CIE) method These upconverted emissions were attributed to a two-photon process. The excitation wavelength dependence of the upconverted luminescence, together with its time evolution after infrared pulsed excitation, suggested that energy transfer upconversion processes were responsible for the upconversion luminescence. The upconversion mechanisms were studied in detail through laser power dependence. Excited state absorption and energy transfer processes were discussed as possible upconversion mechanisms. The cross-relaxation process in Er(3+) was also investigated. Copyright © 2015 John Wiley & Sons, Ltd.

Investigating the evolution of local structure around Er and Yb in ZnO:Er and ZnO:Er, Yb on annealing using X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Anjana, R.; Jayaraj, M. K.; Yadav, A. K.; Jha, S. N.; Bhattacharyya, D.

2018-04-01

The local structure around Er and Yb centre in ZnO favouring upconversion luminescence was studied using EXAFS (Extended X-ray absorption fine structure spectroscopy). Due to the ionic radii difference between Zn and Er, Yb ions, the dopants cannot replace Zn in the ZnO lattice properly. Er2O3 and Yb2O3 impurity phases are formed at the grain boundaries of ZnO. It is found that the local structure around the Er centre in ZnO is modified on annealing in air. The symmetry around both erbium and ytterbium reduces with increase in annealing temperature. Symmetry reduction will favour the intra-4f transition and the energy transitions causing upconversion luminescence. By fitting the EXAFS data with theoretically simulated data, it is found that the Er centre forms a local structure similar to C4ν symmetry which is a distorted octahedron. On annealing the sample to 1200 °C, all the erbium centres are transformed to C4ν symmetry causing enhanced upconversion emission. Yb centre has also been modified on annealing. The decrease in co-ordination number with annealing temperature will decrease the symmetry and increase the near infrared absorption cross section. The decrease in symmetry around both the erbium and ytterbium centre and formation of C4ν symmetry around Er centre is the reason behind the activation of upconversion luminescence with high temperature annealing in both Er doped and Er, Yb co-doped ZnO samples. The study will be useful for the synthesis of high efficiency upconversion materials.

A novel contrast agent with rare earth-doped up-conversion luminescence and Gd-DTPA magnetic resonance properties

NASA Astrophysics Data System (ADS)

Lu, Qing; Wei, Daixu; Cheng, Jiejun; Xu, Jianrong; Zhu, Jun

2012-08-01

The magnetic-luminescent multifunctional nanoparticles based on Gd-DTPA and NaYF4:Yb, Er were successfully synthesized by the conjugation of activated DTPA and silica-coated/surface-aminolated NaYF4:Yb, Er nanoparticles through EDC/NHS coupling chemistry. The as-prepared products were characterized by powder X-ray diffraction, transmission electron microscopy, dynamic light scattering, energy dispersive X-ray analysis, and fourier transform infrared spectrometry. The room-temperature upconversion luminescent spectra and T1-weighted maps of the obtained nanoparticles were carried out by 980 nm NIR light excitation and a 3T MR imaging scanner, respectively. The results indicated that the as-synthesized multifunctional nanoparticles with small size, highly solubility in water, and both high MR relaxivities and upconversion luminescence may have potential usage for MR imaging in future.

Ultrafast mid-infrared spectroscopy by chirped pulse upconversion in 1800-1000cm(-1) region.

PubMed

Zhu, Jingyi; Mathes, Tilo; Stahl, Andreas D; Kennis, John T M; Groot, Marie Louise

2012-05-07

Broadband femtosecond mid-infrared pulses can be converted into the visible spectral region by chirped pulse upconversion. We report here the upconversion of pump probe transient signals in the frequency region below 1800cm(-1), using the nonlinear optical crystal AgGaGeS4, realizing an important expansion of the application range of this method. Experiments were demonstrated with a slab of GaAs, in which the upconverted signals cover a window of 120cm(-1), with 1.5cm(-1) resolution. In experiments on the BLUF photoreceptor Slr1694, signals below 1 milliOD were well resolved after baseline correction. Possibilities for further optimization of the method are discussed. We conclude that this method is an attractive alternative for the traditional MCT arrays used in most mid-infrared pump probe experiments.

Gold decorated NaYF4:Yb,Er/NaYF4/silica (core/shell/shell) upconversion nanoparticles for photothermal destruction of BE(2)-C neuroblastoma cells

NASA Astrophysics Data System (ADS)

Qian, Li Peng; Zhou, Li Han; Too, Heng-Phon; Chow, Gan-Moog

2011-02-01

Gold decorated NaYF4:Yb,Er/NaYF4/silica (core/shell/shell) upconversion (UC) nanoparticles ( 70-80 nm) were synthesized using tetraethyl orthosilicate and chloroauric acid in a one-step reverse microemulsion method. Gold nanoparticles ( 6 nm) were deposited on the surface of silica shell of these core/shell/shell nanoparticles. The total upconversion emission intensity (green, red, and blue) of the core/shell/shell nanoparticles decreased by 31% after Au was deposited on the surface of silica shell. The upconverted green light was coupled with the surface plasmon of Au leading to rapid heat conversion. These UC/silica/Au nanoparticles were very efficient to destroy BE(2)-C cancer cells and showed strong potential in photothermal therapy.

Near infrared harvesting dye-sensitized solar cells enabled by rare-earth upconversion materials.

PubMed

Li, Deyang; Ågren, Hans; Chen, Guanying

2018-02-01

Dye-sensitized solar cells (DSSCs) have been deemed as promising alternatives to silicon solar cells for the conversion of clean sunlight energy into electricity. A major limitation to their conversion efficiency is their inability to utilize light in the infrared (IR) spectral range, which constitutes almost half the energy of the sun's radiation. This fact has elicited motivations and endeavors to extend the response wavelength of DSSCs to the IR range. Photon upconversion through rare-earth ions constitutes one of the most promising approaches toward the goal of converting near-IR (NIR) or IR light into visible or ultraviolet light, where DSSCs typically have high sensitivity. In the present review, we summarize recent progress based on the utilization of various upconversion materials and device structures to improve the performance of dye-sensitized solar cells.

Intense green and red upconversion emission of Er3+,Yb3+ co-doped CaZrO3 obtained by a solution combustion reaction

NASA Astrophysics Data System (ADS)

Singh, Vijay; Kumar Rai, Vineet; Haase, Markus

2012-09-01

CaZrO3 phosphors co-doped with Er3+ and Yb3+ ions have been prepared by the urea combustion route. The formation of the orthorhombic phase of CaZrO3 was confirmed by powder x-ray diffraction. The absorption in the 280-1800 nm region and excitation spectrum corresponding to the emission at 545 nm for CaZrO3:Er3+/CaZrO3:Er3+,Yb3+ phosphors have been recorded. Upon excitation at 978 nm, the material displays strong energy transfer upconversion emission in the green and red spectral regions. The upconversion emission of the CaZrO3:Er3+,Yb3+ co-doped material shows an increased red-to-green ratio, indicating cross relaxation between Er3+ ions.

Methods of making functionalized nanorods

DOEpatents

Gur, Ilan [San Francisco, CA; Milliron, Delia [Berkeley, CA; Alivisatos, A Paul [Oakland, CA; Liu, Haitao [Berkeley, CA

2012-01-10

A process for forming functionalized nanorods. The process includes providing a substrate, modifying the substrate by depositing a self-assembled monolayer of a bi-functional molecule on the substrate, wherein the monolayer is chosen such that one side of the bi-functional molecule binds to the substrate surface and the other side shows an independent affinity for binding to a nanocrystal surface, so as to form a modified substrate. The process further includes contacting the modified substrate with a solution containing nanocrystal colloids, forming a bound monolayer of nanocrystals on the substrate surface, depositing a polymer layer over the monolayer of nanocrystals to partially cover the monolayer of nanocrystals, so as to leave a layer of exposed nanocrystals, functionalizing the exposed nanocrystals, to form functionalized nanocrystals, and then releasing the functionalized nanocrystals from the substrate.

Conjugated polymer/nanocrystal nanocomposites for renewable energy applications in photovoltaics and photocatalysis.

PubMed

Su, Yu-Wei; Lin, Wei-Hao; Hsu, Yung-Jung; Wei, Kung-Hwa

2014-11-01

Conjugated polymer/nanocrystal composites have attracted much attention for use in renewable energy applications because of their versatile and synergistic optical and electronic properties. Upon absorbing photons, charge separation occurs in the nanocrystals, generating electrons and holes for photocurrent flow or reduction/oxidation (redox) reactions under proper conditions. Incorporating these nanocrystals into conjugated polymers can complement the visible light absorption range of the polymers for photovoltaics applications or allow the polymers to sensitize or immobilize the nanocrystals for photocatalysis. Here, the current developments of conjugated polymer/nanocrystal nanocomposites for bulk heterojunction-type photovoltaics incorporating Cd- and Pb-based nanocrystals or quantum dots are reviewed. The effects of manipulating the organic ligands and the concentration of the nanocrystal precursor, critical factors that affect the shape and aggregation of the nanocrystals, are also discussed. In the conclusion, the mechanisms through which conjugated polymers can sensitize semiconductor nanocrystals (TiO2 , ZnO) to ensure efficient charge separation, as well as how they can support immobilized nanocrystals for use in photocatalysis, are addressed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deep Photoacoustic/Luminescence/Magnetic Resonance Multimodal Imaging in Living Subjects Using High-Efficiency Upconversion Nanocomposites.

PubMed

Liu, Yu; Kang, Ning; Lv, Jing; Zhou, Zijian; Zhao, Qingliang; Ma, Lingceng; Chen, Zhong; Ren, Lei; Nie, Liming

2016-08-01

A gadolinium-doped multi-shell upconversion nanoparticle under 800 nm excitation is synthesized with a 10-fold fluorescence-intensity enhancement over that under 980 nm. The nanoformulations exhibit excellent photoacoustic/luminescence/magnetic resonance tri-modal imaging capabilities, enabling visualization of tumor morphology and microvessel distribution at a new imaging depth. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyropheophorbide A and c(RGDyK) comodified chitosan-wrapped upconversion nanoparticle for targeted near-infrared photodynamic therapy.

PubMed

Zhou, Aiguo; Wei, Yanchun; Wu, Baoyan; Chen, Qun; Xing, Da

2012-06-04

Near-infrared (NIR)-to-visible upconversion nanoparticle (UCNP) has shown promising prospects in photodynamic therapy (PDT) as a drug carrier or energy donor. In this work, a photosensitizer pyropheophorbide a (Ppa) and RGD peptide c(RGDyK) comodified chitosan-wrapped NaYF(4):Yb/Er upconversion nanoparticle UCNP-Ppa-RGD was developed for targeted near-infrared photodynamic therapy. The properties of UCNP-Ppa-RGD, such as morphology, stability, optical spectroscopy and singlet oxygen generation efficiency, were investigated. The results show that covalently linked pyropheophorbide a molecule not only is stable but also retains its spectroscopic and functional properties. In vitro studies confirm a stronger targeting specificity of UCNP-Ppa-RGD to integrin α(v)β(3)-positive U87-MG cells compared with that in the corresponding negative group. The photosensitizer-attached nanostructure exhibited low dark toxicity and high phototoxicity against cancer cells upon 980 nm laser irradiation at an appropriate dosage. These results represent the first demonstration of a highly stable and efficient photosensitizer modified upconversion nanostructure for targeted near-infrared photodynamic therapy of cancer cells. The novel UCNP-Ppa-RGD nanoparticle may provide a powerful alternative for near-infrared photodynamic therapy with an improved tumor targeting specificity.

The Intersection of CMOS Microsystems and Upconversion Nanoparticles for Luminescence Bioimaging and Bioassays

PubMed Central

Wei, Liping.; Doughan, Samer.; Han, Yi.; DaCosta, Matthew V.; Krull, Ulrich J.; Ho, Derek.

2014-01-01

Organic fluorophores and quantum dots are ubiquitous as contrast agents for bio-imaging and as labels in bioassays to enable the detection of biological targets and processes. Upconversion nanoparticles (UCNPs) offer a different set of opportunities as labels in bioassays and for bioimaging. UCNPs are excited at near-infrared (NIR) wavelengths where biological molecules are optically transparent, and their luminesce in the visible and ultraviolet (UV) wavelength range is suitable for detection using complementary metal-oxide-semiconductor (CMOS) technology. These nanoparticles provide multiple sharp emission bands, long lifetimes, tunable emission, high photostability, and low cytotoxicity, which render them particularly useful for bio-imaging applications and multiplexed bioassays. This paper surveys several key concepts surrounding upconversion nanoparticles and the systems that detect and process the corresponding luminescence signals. The principle of photon upconversion, tuning of emission wavelengths, UCNP bioassays, and UCNP time-resolved techniques are described. Electronic readout systems for signal detection and processing suitable for UCNP luminescence using CMOS technology are discussed. This includes recent progress in miniaturized detectors, integrated spectral sensing, and high-precision time-domain circuits. Emphasis is placed on the physical attributes of UCNPs that map strongly to the technical features that CMOS devices excel in delivering, exploring the interoperability between the two technologies. PMID:25211198

Efficient upconversion-pumped continuous wave Er3+:LiLuF4 lasers

NASA Astrophysics Data System (ADS)

Moglia, Francesca; Müller, Sebastian; Reichert, Fabian; Metz, Philip W.; Calmano, Thomas; Kränkel, Christian; Heumann, Ernst; Huber, Günter

2015-04-01

We report on detailed spectroscopic investigations and efficient visible upconversion laser operation of Er3+:LiLuF4. This material allows for efficient resonant excited-state-absorption (ESA) pumping at 974 nm. Under spectroscopic conditions without external feedback, ESA at the laser wavelength of 552 nm prevails stimulated emission. Under lasing conditions in a resonant cavity, the high intracavity photon density bleaches the ESA at 552 nm, allowing for efficient cw laser operation. We obtained the highest output power of any room-temperature crystalline upconversion laser. The laser achieves a cw output power of 774 mW at a slope efficiency of 19% with respect to the incident pump power delivered by an optically-pumped semiconductor laser. The absorption efficiency of the pump radiation is estimated to be below 50%. To exploit the high confinement in waveguides for this laser, we employed femtosecond-laser pulses to inscribe a cladding of parallel tracks of modified material into Er3+:LiLuF4 crystals. The core material allows for low-loss waveguiding at pump and laser wavelengths. Under Ti:sapphire pumping at 974 nm, the first crystalline upconversion waveguide laser has been realized. We obtained waveguide-laser operation with up to 10 mW of output power at 553 nm.

Yb3+/Ho3+ Co-Doped Apatite Upconversion Nanoparticles to Distinguish Implanted Material from Bone Tissue.

PubMed

Li, Xiyu; Chen, Haifeng

2016-10-07

The exploration of bone reconstruction with time requires the combination of a biological method and a chemical technique. Lanthanide Yb 3+ and Ho 3+ co-doped fluorapatite (FA:Yb 3+ /Ho 3+ ) and hydroxyapatite (HA:Yb 3+ /Ho 3+ ) particles with varying dopant concentrations were prepared by hydrothermal synthesis and thermal activation. Controllable green and red upconversion emissions were generated under 980 nm near-infrared excitation; the FA:Yb 3+ /Ho 3+ particles resulted in superior green luminescence, while HA:Yb 3+ /Ho 3+ dominated in red emission. The difference in the green and red emission behavior was dependent on the lattice structure and composition. Two possible lattice models were proposed for Yb 3+ /Ho 3+ co-doped HA and FA along the hydroxyl channel and fluorine channel of the apatite crystal structure. We first reported the use of the upconversion apatite particles to clearly distinguish implanted material from bone tissue on stained histological sections of harvested in vivo samples. The superposition of the tissue image and material image is a creative method to show the material-tissue distribution and interrelation. The upconversion apatite particles and image superposition method provide a novel strategy for long-term discriminable fluorescence tracking of implanted material or scaffold during bone regeneration.

Synergistic plasmonic and photonic crystal light-trapping: architectures for optical up-conversion in thin-film solar cells.

PubMed

Le, Khai Q; John, Sajeev

2014-01-13

We demonstrate, numerically, that with a 60 nanometer layer of optical up-conversion material, embedded with plasmonic core-shell nano-rings and placed below a sub-micron silicon conical-pore photonic crystal it is possible to absorb sunlight well above the Lambertian limit in the 300-1100 nm range. With as little as 500 nm, equivalent bulk thickness of silicon, the maximum achievable photo-current density (MAPD) is about 36 mA/cm2, using above-bandgap sunlight. This MAPD increases to about 38 mA/cm2 for one micron of silicon. Our architecture also provides solar intensity enhancement by a factor of at least 1400 at the sub-bandgap wavelength of 1500 nm, due to plasmonic and photonic crystal resonances, enabling a further boost of photo-current density from up-conversion of sub-bandgap sunlight. With an external solar concentrator, providing 100 suns, light intensities sufficient for significant nonlinear up-conversion can be realized. Two-photon absorption of sub-bandgap sunlight is further enhanced by the large electromagnetic density of states in the photonic crystal at the re-emission wavelength near 750 nm. It is suggested that this synergy of plasmonic and photonic crystal resonances can lead to unprecedented power conversion efficiency in ultra-thin-film silicon solar cells.

Composite material including nanocrystals and methods of making

DOEpatents

Bawendi, Moungi G.; Sundar, Vikram C.

2010-04-06

Temperature-sensing compositions can include an inorganic material, such as a semiconductor nanocrystal. The nanocrystal can be a dependable and accurate indicator of temperature. The intensity of emission of the nanocrystal varies with temperature and can be highly sensitive to surface temperature. The nanocrystals can be processed with a binder to form a matrix, which can be varied by altering the chemical nature of the surface of the nanocrystal. A nanocrystal with a compatibilizing outer layer can be incorporated into a coating formulation and retain its temperature sensitive emissive properties.

Composite material including nanocrystals and methods of making

DOEpatents

Bawendi, Moungi G [Boston, MA; Sundar, Vikram C [New York, NY

2008-02-05

Temperature-sensing compositions can include an inorganic material, such as a semiconductor nanocrystal. The nanocrystal can be a dependable and accurate indicator of temperature. The intensity of emission of the nanocrystal varies with temperature and can be highly sensitive to surface temperature. The nanocrystals can be processed with a binder to form a matrix, which can be varied by altering the chemical nature of the surface of the nanocrystal. A nanocrystal with a compatibilizing outer layer can be incorporated into a coating formulation and retain its temperature sensitive emissive properties

Ultrasonication of Bismuth Telluride Nanocrystals Fabricated by Solvothermal Method

NASA Technical Reports Server (NTRS)

Chu, Sang-Hyon; Choi, Sang H.; Kim, Jae-Woo; King, Glen C.; Elliott, James R.

2006-01-01

The objective of this study is to evaluate the effect of ultrasonication on bismuth telluride nanocrystals prepared by solvothermal method. In this study, a low dimensional nanocrystal of bismuth telluride (Bi2Te3) was synthesized by a solvothermal process in an autoclave at 180 C and 200 psi. During the solvothermal reaction, organic surfactants effectively prevented unwanted aggregation of nanocrystals in a selected solvent while controlling the shape of the nanocrystal. The atomic ratio of bismuth and tellurium was determined by energy dispersive spectroscopy (EDS). The cavitational energy created by the ultrasonic probe was varied by the ultrasonication process time, while power amplitude remained constant. The nanocrystal size and its size distribution were measured by field emission scanning electron microscopy (FESEM) and a dynamic light scattering system. When the ultrasonication time increased, the average size of bismuth telluride nanocrystal gradually increased due to the direct collision of nanocrystals. The polydispersity of the nanocrystals showed a minimum when the ultrasonication was applied for 5 min. Keywords: bismuth telluride, nanocrystal, low-dimensional, ultrasonication, solvothermal

Nimodipine nanocrystals for oral bioavailability improvement: preparation, characterization and pharmacokinetic studies.

PubMed

Fu, Qiang; Sun, Jin; Zhang, Dong; Li, Mo; Wang, Yongjun; Ling, Guixia; Liu, Xiaohong; Sun, Yinghua; Sui, Xiaofan; Luo, Cong; Sun, Le; Han, Xiaopeng; Lian, He; Zhu, Meng; Wang, Siling; He, Zhonggui

2013-09-01

This study intended to develop nimodipine (NMD) nanocrystals with different sizes for oral administration and to investigate the relationship between dissolution and pharmacokinetics for NMD nanocrystals and Nimotop(®). NMD nanocrystals were prepared by combination of microprecipitation and high pressure homogenization and were further lyophilized. The particle size, morphology and aqueous solubility of the NMD nanocrystals were determined. With Nimotop(®) as the control, the dissolution rate was evaluated and the pharmacokinetic study was undertaken in beagle dogs. NMD nanocrystals with mean diameters of about 159.0, 503.0 and 833.3 nm were prepared, respectively. The lyophilization didn't affect the particle sizes of the redispersed nanocrystals. The aqueous solubility was significantly improved and displayed a size-dependent manner. The nanocrystals exhibited lower dissolution patterns than Nimotop(®) under non-sink condition, but bioavailability of the two nanocrystals (159.0 and 833.3 nm) was equivalent, about 2.6-fold higher than Nimotop(®). In conclusion, oral nanocrystal drug delivery system was a promising strategy in improving the oral bioavailability of poorly soluble or insoluble drugs. But we could not establish a favorable in vitro in vivo correlation for NMD nanocrystals and Nimotop(®) and thus the oral absorption mechanism of the NMD nanocrystals required further study. Copyright © 2013 Elsevier B.V. All rights reserved.

Electron transfer between colloidal ZnO nanocrystals.

PubMed

Hayoun, Rebecca; Whitaker, Kelly M; Gamelin, Daniel R; Mayer, James M

2011-03-30

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.

Nanocrystal structures

DOEpatents

Eisler, Hans J [Stoneham, MA; Sundar, Vikram C [Stoneham, MA; Walsh, Michael E [Everett, MA; Klimov, Victor I [Los Alamos, NM; Bawendi, Moungi G [Cambridge, MA; Smith, Henry I [Sudbury, MA

2008-12-30

A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II-VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

Nanocrystal structures

DOEpatents

Eisler, Hans J.; Sundar, Vikram C.; Walsh, Michael E.; Klimov, Victor I.; Bawendi, Moungi G.; Smith, Henry I.

2006-12-19

A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II–VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

Optical properties of silicon nanocrystals synthesized in supercritical fluids

NASA Astrophysics Data System (ADS)

Pell, Lindsay; Korgel, Brian A.

2002-11-01

We developed a supercritical solution phase synthesis of silicon nanocrystals. High temperature and pressure (500°C, >140 bar) conditions allow a wet chemical approach to this challenging synthesis. Diphenylsilane was used as a silicon precursor and long chain thiols and alcohols were used to sterically stabilize the luminescent nanocrystals. Moderate size separation was achieved via size exclusion chromatography using crosslinked styrene divinylbenzene beads. Size separated fractions of silicon nanocrystals exhibit quantum efficiencies of 12% while polydisperse samples have quantum efficiencies of 5%. Nanocrystal size distributions have been determined with transmission electron microscopy and further characterized with atomic force microscopy (AFM). These silicon nanocrystals have size tunable photoluminescence as indicated by their ensemble spectroscopy and further verified through AFM and single nanocrystal photoluminescence spectroscopy. Fluorescence intermittency (characteristic of single CdSe nanocrystals) is present in our isolated silicon nanocrystals and is one of the criteria used to distinguish single crystals from clusters of particles.

State of the art of nanocrystals technology for delivery of poorly soluble drugs

NASA Astrophysics Data System (ADS)

Zhou, Yuqi; Du, Juan; Wang, Lulu; Wang, Yancai

2016-09-01

Formulation of nanocrystals is a distinctive approach which can effectively improve the delivery of poorly water-soluble drugs, thus enticing the development of the nanocrystals technology. The characteristics of nanocrystals resulted in an exceptional drug delivery conductance, including saturation solubility, dissolution velocity, adhesiveness, and affinity. Nanocrystals were treated as versatile pharmaceuticals that could be delivered through almost all routes of administration. In the current review, oral, pulmonary, and intravenous routes of administration were presented. Also, the targeting of drug nanocrystals, as well as issues of efficacy and safety, were also discussed. Several methods were applied for nanocrystals production including top-down production strategy (media milling, high-pressure homogenization), bottom-up production strategy (antisolvent precipitation, supercritical fluid process, and precipitation by removal of solvent), and the combination approaches. Moreover, this review also described the evaluation and characterization of the drug nanocrystals and summarized the current commercial pharmaceutical products utilizing nanocrystals technology.

Nanocrystals Technology for Pharmaceutical Science.

PubMed

Cheng, Zhongyao; Lian, Yumei; Kamal, Zul; Ma, Xin; Chen, Jianjun; Zhou, Xinbo; Su, Jing; Qiu, Mingfeng

2018-05-17

Nanocrystals technology is a promising method for improving the dissolution rate and enhancing the bioavailability of poorly soluble drugs. In recent years, it has been developing rapidly and applied to drug research and engineering. Nanocrystal drugs can be formulated into various dosage forms. This review mainly focused on the nanocrystals technology and its application in pharmaceutical science. Firstly, different preparation methods of nanocrystal technology and the characterization of nanocrystal drugs are briefly described. Secondly, the application of nanocrystals technology in pharmaceutical science is mainly discussed followed by the introduction of sustained release formulations. Then, the scaling up process, marketed nanocrystal drug products and regulatory aspects about nanodrugs are summarized. Finally, the specific challenges and opportunities of nanocrystals technology for pharmaceutical science are summarized and discussed. This review will provide a comprehensive guide for scientists and engineers in the field of pharmaceutical science and biochemical engineering. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Colloidal Nanocrystals with Near-infrared Optical Properties: Synthesis, Characterization, and Applications

NASA Astrophysics Data System (ADS)

Panthani, Matthew George

2011-07-01

Colloidal nanocrystals with optical properties in the near-infrared (NIR) are of interest for many applications such as photovoltaic (PV) energy conversion, bioimaging, and therapeutics. For PVs and other electronic devices, challenges in using colloidal nanomaterials often deal with the surfaces. Because of the high surface-to-volume ratio of small nanocrystals, surfaces and interfaces play an enhanced role in the properties of nanocrystal films and devices. Organic ligand-capped CuInSe2 (CIS) and Cu(InXGa 1-X)Se2 (CIGS) nanocrystals were synthesized and used as the absorber layer in prototype solar cells. By fabricating devices from spray-coated CuInSe nanocrystals under ambient conditions, solar-to-electric power conversion efficiencies as high as 3.1% were achieved. Many treatments of the nanocrystal films were explored. Although some treatments increased the conductivity of the nanocrystal films, the best devices were from untreated CIS films. By modifying the reaction chemistry, quantum-confined CuInSe XS2-X (CISS) nanocrystals were produced. The potential of the CISS nanocrystals for targeted bioimaging was demonstrated via oral delivery to mice and imaging of nanocrystal fluorescence. The size-dependent photoluminescence of Si nanocrystals was measured. Si nanocrystals supported on graphene were characterized by conventional transmission electron microscopy and spherical aberration (Cs)-corrected scanning transmission electron microscopy (STEM). Enhanced imaging contrast and resolution was achieved by using Cs-corrected STEM with a graphene support. In addition, clear imaging of defects and the organic-inorganic interface was enabled by utilizing this technique.

Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

NASA Astrophysics Data System (ADS)

Lynch, Jared James

Colloidal inorganic nanocrystals are a class of material whose size ranges from a few nanometers to a hundred nanometers in dimension. These nanocrystals have size dependent properties that differ significantly from the bulk material counterparts. Due to their unique physical properties colloidal inorganic nanocrystals have several promising applications in a diverse range of areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents the study of the formation of iron oxide nanocrystals under the influence of solvent and Ar gas bubbles, the phase transfer of metal oxide nanocrystals into water using inorganic ions, and the doping of semiconductor CdS/ZnS core/shell nanocrystals with copper and silver ions. First, the formation of iron oxide nanocrystals is investigated in the presence of boiling solvent or Ar bubbles. Using a non-injection based synthesis method, the thermal decomposition of iron oleate was studied under various reaction conditions, and the role of the bubbles on the nucleation and growth of iron oxide nanocrystals was determined. Kinetics studies were used to elucidate how latent heat transfer from the bubbles allows for "active monomers" to form preferentially from exothermic reactions taking place during nucleation. General insights into colloidal inorganic nanocrystal formation are discussed. Second, a non-injection based synthesis for CdS/ZnS core/shell nanocrystals is used to make high quality semiconductor particles which are intentionally doped with Cu or Ag ions. The Ag ions effect on the optical properties of the CdS/ZnS nanocrystals is investigated. The absorption and fluorescence of the samples is measured as a function of time and temperature. Proposed mechanisms for the observations are given and thoroughly discussed. Comparisons between previous results for Cu doped CdS/ZnS nanocrystals are also made to further understand how doping of semiconductor nanocrystals can be realized. Finally, a novel phase transfer process is demonstrated using inorganic salts, such as sodium arsenite, to make water soluble metal oxide nanocrystals. The water soluble iron oxide nanocrystals are fully characterized by several complementary techniques and then used in cellular studies. The arsenite-coated iron oxide composite nanocrystals (AICN) are shown to be effective cancer therapy agents.

Synchronous and noncollinear infrared upconversion in AgGaS/sub 2/. [JERRY 0999; JERRY 0998; JERRY 1111

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhar, G.C.; Das, S.; Chatterjee, U.

1989-04-17

Synchronous noncollinear upconversion detection is reported for the first time with a Nd:YAG laser in AgGaS/sub 2/. Q-switched pump laser pulses with a repetition rate up to 50 Hz were synchronized with intracavity chopped continuous wave CO/sub 2/ laser pulses. Results were obtained both by tuning the CO/sub 2/ laser and by varying the angle between the laser beams.

Detection of telomerase on upconversion nanoparticle modified cellulose paper.

PubMed

Wang, Faming; Li, Wen; Wang, Jiasi; Ren, Jinsong; Qu, Xiaogang

2015-07-25

Herein we report a convenient and sensitive method for the detection of telomerase activity based on upconversion nanoparticle (UCNP) modified cellulose paper. Compared with many solution-phase systems, this paper chip is more stable and easily stores the test results. What's more, the low background fluorescence of the UCNPs increases the sensitivity of this method, and the low telomerase levels in different cell lines can clearly be discriminated by the naked eye.

Tunable green/red luminescence by infrared upconversion in biocompatible forsterite nanoparticles with high erbium doping uptake

NASA Astrophysics Data System (ADS)

Zampiva, Rúbia Young Sun; Acauan, Luiz Henrique; Venturini, Janio; Garcia, Jose Augusto Martins; da Silva, Diego Silverio; Han, Zhaohong; Kassab, Luciana Reyes Pires; Wetter, Niklaus Ursus; Agarwal, Anuradha; Alves, Annelise Kopp; Bergmann, Carlos Pérez

2018-02-01

Nanoparticles represent a promising platform for diagnostics and therapy of human diseases. For biomedical applications, these nanoparticles are usually coated with photosensitizers regularly activated in a spectral window of 530-700 nm. The emissions at 530 nm (green) and 660 nm (red) are of particular interest for imaging and photodynamic therapy, respectively. This work presents the Mg2SiO4:Er3+ system, produced by reverse strike co-precipitation, with up to 10% dopant and no secondary phase formation. These nanoparticles when excited at 985 nm show upconversion emission with peaks around 530 and 660 nm, although excitation at 808 nm leads to only a single emission peak at around 530 nm. The direct upconversion of this biomaterial without a co-dopant, and its tunability by the excitation source, renders Mg2SiO4:Er3+ nanoparticles a promising system for biomedical applications.

Molecular approaches to third generation photovoltaics: photochemical up-conversion

NASA Astrophysics Data System (ADS)

Cheng, Yuen Yap; Fückel, Burkhard; Roberts, Derrick A.; Khoury, Tony; Clady, Rapha"l. G. C. R.; Tayebjee, Murad J. Y.; Piper, Roland; Ekins-Daukes, N. J.; Crossley, Maxwell J.; Schmidt, Timothy W.

2010-08-01

We have investigated a photochemical up-conversion system comprising a molecular mixture of a palladium porphyrin to harvest light, and a polycyclic aromatic hydrocarbon to emit light. The energy of harvested photons is stored as molecular triplet states which then annihilate to bring about up-converted fluorescence. The limiting efficiency of such triplet-triplet annihilation up-conversion has been believed to be 11% for some time. However, by rigorously investigating the kinetics of delayed fluorescence following pulsed excitation, we demonstrate instantaneous annihilation efficiencies exceeding 40%, and limiting efficiencies for the current system of ~60%. We attribute the high efficiencies obtained to the electronic structure of the emitting molecule, which exhibits an exceptionally high T2 molecular state. We utilize the kinetic data obtained to model an up-converting layer irradiated with broadband sunlight, finding that ~3% efficiencies can be obtained with the current system, with this improving dramatically upon optimization of various parameters.

Rich stochastic dynamics of co-doped Er:Yb fluorescence upconversion nanoparticles in the presence of thermal, non-conservative, harmonic and optical forces

NASA Astrophysics Data System (ADS)

Nome, Rene A.; Sorbello, Cecilia; Jobbágy, Matías; Barja, Beatriz C.; Sanches, Vitor; Cruz, Joyce S.; Aguiar, Vinicius F.

2017-03-01

The stochastic dynamics of individual co-doped Er:Yb upconversion nanoparticles (UCNP) were investigated from experiments and simulations. The UCNP were characterized by high-resolution scanning electron microscopy, dynamic light scattering, and zeta potential measurements. Single UCNP measurements were performed by fluorescence upconversion micro-spectroscopy and optical trapping. The mean-square displacement (MSD) from single UCNP exhibited a time-dependent diffusion coefficient which was compared with Brownian dynamics simulations of a viscoelastic model of harmonically bound spheres. Experimental time-dependent two-dimensional trajectories of individual UCNP revealed correlated two-dimensional nanoparticle motion. The measurements were compared with stochastic trajectories calculated in the presence of a non-conservative rotational force field. Overall, the complex interplay of UCNP adhesion, thermal fluctuations and optical forces led to a rich stochastic behavior of these nanoparticles.

Solar-Pumping Upconversion of Interfacial Coordination Nanoparticles.

PubMed

Ishii, Ayumi; Hasegawa, Miki

2017-01-30

An interfacial coordination nanoparticle successfully exhibited an upconversion blue emission excited by very low-power light irradiation, such as sunlight. The interfacial complex was composed of Yb ions and indigo dye, which formed a nano-ordered thin shell layer on a Tm 2 O 3 nanoparticle. At the surface of the Tm 2 O 3 particle, the indigo dye can be excited by non-laser excitation at 640 nm, following the intramolecular energy transfer from the indigo dye to the Yb ions. Additionally, the excitation energy of the Yb ion was upconverted to the blue emission of the Tm ion at 475 nm. This upconversion blue emission was achieved by excitation with a CW Xe lamp at an excitation power of 0.14 mW/cm 2 , which is significantly lower than the solar irradiation power of 1.4 mW/cm 2 at 640 ± 5 nm.

Synthesis of Er(III)/Yb(III)-doped BiF3 upconversion nanoparticles for use in optical thermometry.

PubMed

Du, Peng; Yu, Jae Su

2018-03-23

The authors describe an ethylene glycol assisted precipitation method for synthesis of Er(III)/Yb(III)-doped BiF 3 nanoparticles (NPs) at room temperature. Under 980-nm light irradiation, the NPs emit upconversion (UC) emission of Er(III) ions as a result of a two-photon absorption process. The temperature-dependent green emissions (peaking at 525 and 545 nm) are used to establish an unambiguous relationship between the ratio of fluorescence intensities and temperature. The NPs have a maximum sensitivity of 6.5 × 10 -3  K -1 at 619 K and can be applied over the 291-691 K temperature range. The results indicate that these NPs are a promising candidate for optical thermometry. Graphical abstract Schematic of the room-temperature preparation of Er(III)/Yb(III)-doped BiF 3 nanoparticles with strongly temperature-dependent upconversion emission.

Simultaneous quasi-one-dimensional propagation and tuning of upconversion luminescence through waveguide effect

PubMed Central

Gao, Dangli; Tian, Dongping; Zhang, Xiangyu; Gao, Wei

2016-01-01

Luminescence-based waveguide is widely investigated as a promising alternative to conquer the difficulties of efficiently coupling light into a waveguide. But applications have been still limited due to employing blue or ultraviolet light as excitation source with the lower penetration depth leading to a weak guided light. Here, we show a quasi-one-dimensional propagation of luminescence and then resulting in a strong luminescence output from the top end of a single NaYF4:Yb3+/Er3+ microtube under near infrared light excitation. The mechanism of upconversion propagation, based on the optical waveguide effect accompanied with energy migration, is proposed. The efficiency of luminescence output is highly dependent on the concentration of dopant ions, excitation power, morphology, and crystallinity of tube as an indirect evidence of the existence of the optical actived waveguide effect. These findings provide the possibility for the construction of upconversion fiber laser. PMID:26926491

Tuning sputtered gold thickness to enhance absorption and emission in core-shell type erbium doped upconversion nanoparticles

NASA Astrophysics Data System (ADS)

Manurung, R. V.; Wu, C. T.; Chattopadhyay, S.

2018-03-01

Upconversion nanoparticles (UCNPs) converts near-infrared excitation to visible emission with advantages e.g. photostable, non-blinking, and background-free probes for bioimaging and biosensor. However, low quantum yield and low efficiency (∼1%) as drawback need to be enhanced. A plasmonic gold nano-structured surface was designed and fabricated to couple with the 980 nm radiation and produce plasmonic enhancement of the upconversion luminescence. The synthesis of the UCNPs was done by thermal decomposition and SiO2 coating prepared by the reverse microemulsion process. Here, we report a novel tunable plasmon-enhanced fluorescence by modulating the thickness and surface roughness of gold island film on Si. The localized surface plasmon resonance (LSPR) at 980 nm was obtained, matched with the native excitation of UCNPs resulting in maximum enhancement of 10-fold of green emission band at 540 nm for the Er-doped UCNPs.

Spectroscopy and visible frequency upconversion in Er3+-Yb3+: TeO2-ZnO glass.

PubMed

Mohanty, Deepak Kumar; Rai, Vineet Kumar

2014-01-01

The UV-Vis-NIR absorption studies of the Er(3+)/Er(3+)-Yb(3+) doped/codoped TeO2-ZnO (TZO) glasses fabricated by the melting and quenching method has been performed. The spectroscopic radiative parameters viz. radiative transition probabilities, branching ratios and lifetimes have been determined from the absorption spectrum by using Judd-Ofelt theory. The near infrared (NIR) to visible frequency upconversion (UC) have been monitored by using an excitation of 976 nm wavelength radiation from a CW diode laser. The effect of codoping with Yb(3+) ions on the intensity of the UC emission bands from the Er(3+) ions throughout visible region has been studied. The mechanism responsible for the observed upconversion emissions in the prepared samples have been explained on the basis of excited state absorption and efficient energy transfer processes. Copyright © 2013 Elsevier B.V. All rights reserved.

Evaluation of the upconversion mechanisms in Ho3+-doped crystals: Experiment and theoretical modeling

NASA Astrophysics Data System (ADS)

Osiac, E.; Sokólska, I.; Kück, S.

2002-06-01

The paper compares the mechanisms that enable the upconverted green emission (5S2-->5I8) of the Ho3+ ion under infrared excitation (700-920 nm) in several crystalline hosts (YAlO3, YLiF4, Y3Sc2Ga3O12, and BaY2F8). Parameters involved in the upconversion such as excited-state absorption and cross-relaxation rates were determined from spectroscopic measurements. A system of differential equation (rate equations) was used to describe the upconversion mechanism and was numerically solved. The results were compared with experimental data. A reduction of this system to a three-level ``simplified system'' is presented, which includes only the ground level, the emitting level, and the intermediate level. The differences between the photon-avalanche mechanism and the looping mechanism are discussed and analyzed according to this simplified system.

Field trial of differential-phase-shift quantum key distribution using polarization independent frequency up-conversion detectors.

PubMed

Honjo, T; Yamamoto, S; Yamamoto, T; Kamada, H; Nishida, Y; Tadanaga, O; Asobe, M; Inoue, K

2007-11-26

We report a field trial of differential phase shift quantum key distribution (QKD) using polarization independent frequency up-conversion detectors. A frequency up-conversion detector is a promising device for achieving a high key generation rate when combined with a high clock rate QKD system. However, its polarization dependence prevents it from being applied to practical QKD systems. In this paper, we employ a modified polarization diversity configuration to eliminate the polarization dependence. Applying this method, we performed a long-term stability test using a 17.6-km installed fiber. We successfully demonstrated stable operation for 6 hours and achieved a sifted key generation rate of 120 kbps and an average quantum bit error rate of 3.14 %. The sifted key generation rate was not the estimated value but the effective value, which means that the sifted key was continuously generated at a rate of 120 kbps for 6 hours.

Simultaneous multiple wavelength upconversion in a core-shell nanoparticle for enhanced near infrared light harvesting in a dye-sensitized solar cell.

PubMed

Yuan, Chunze; Chen, Guanying; Li, Lin; Damasco, Jossana A; Ning, Zhijun; Xing, Hui; Zhang, Tianmu; Sun, Licheng; Zeng, Hao; Cartwright, Alexander N; Prasad, Paras N; Ågren, Hans

2014-10-22

The efficiency of most photovoltaic devices is severely limited by near-infrared (NIR) transmission losses. To alleviate this limitation, a new type of colloidal upconversion nanoparticles (UCNPs), hexagonal core-shell-structured β-NaYbF4:Er(3+)(2%)/NaYF4:Nd(3+)(30%), is developed and explored in this work as an NIR energy relay material for dye-sensitized solar cells (DSSCs). These UCNPs are able to harvest light energy in multiple NIR regions, and subsequently convert the absorbed energy into visible light where the DSSCs strongly absorb. The NIR-insensitive DSSCs show compelling photocurrent increases through binary upconversion under NIR light illumination either at 785 or 980 nm, substantiating efficient energy relay by these UCNPs. The overall conversion efficiency of the DSSCs was improved with the introduction of UCNPs under simulated AM 1.5 solar irradiation.

Upconversion luminescence from Er-N codoped of ZnO nanowires prepared by ion implantation method

NASA Astrophysics Data System (ADS)

Zhong, Kun; Xu, Jie; Su, Jing; Chen, Yu lin

2011-02-01

Nitrogen and erbium co-doped of ZnO nanowires (NWs) are fabricated by ion implantation and subsequent annealing in air. The incorporation of Er3+ and N+ ions is verified by energy dispersive X-ray spectroscopy (EDS) and Raman spectra. The samples exhibit upconversion photoluminescence around ∼550 nm and ∼660 nm under an excitation at 980 nm. It is discovered that the N-doped can drastically increase the upconversion photoluminescence intensity by modifying the local structure around Er3+ in ZnO matrix. The enhancement of the PL intensity by the N-doped is caused by the formation of ErO6-xNx octahedron complexes. With the increase of the annealing temperature (Ta), the Er3+ ions diffuse towards the surface of the NWs, which benefits the red emission and evokes the variation of intensity ratio owing to the existence of some organic groups.

Process for forming shaped group III-V semiconductor nanocrystals, and product formed using process

DOEpatents

Alivisatos, A. Paul; Peng, Xiaogang; Manna, Liberato

2001-01-01

A process for the formation of shaped Group III-V semiconductor nanocrystals comprises contacting the semiconductor nanocrystal precursors with a liquid media comprising a binary mixture of phosphorus-containing organic surfactants capable of promoting the growth of either spherical semiconductor nanocrystals or rod-like semiconductor nanocrystals, whereby the shape of the semiconductor nanocrystals formed in said binary mixture of surfactants is controlled by adjusting the ratio of the surfactants in the binary mixture.

Process for forming shaped group II-VI semiconductor nanocrystals, and product formed using process

DOEpatents

Alivisatos, A. Paul; Peng, Xiaogang; Manna, Liberato

2001-01-01

A process for the formation of shaped Group II-VI semiconductor nanocrystals comprises contacting the semiconductor nanocrystal precursors with a liquid media comprising a binary mixture of phosphorus-containing organic surfactants capable of promoting the growth of either spherical semiconductor nanocrystals or rod-like semiconductor nanocrystals, whereby the shape of the semiconductor nanocrystals formed in said binary mixture of surfactants is controlled by adjusting the ratio of the surfactants in the binary mixture.

High-temperature crystallization of nanocrystals into three-dimensional superlattices.

PubMed

Wu, Liheng; Willis, Joshua J; McKay, Ian Salmon; Diroll, Benjamin T; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J

2017-08-10

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.

High-temperature crystallization of nanocrystals into three-dimensional superlattices

NASA Astrophysics Data System (ADS)

Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; Diroll, Benjamin T.; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J.

2017-08-01

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.

The Use of Cellulose Nanocrystals for Potential Application in Topical Delivery of Hydroquinone.

PubMed

Taheri, Azade; Mohammadi, Mina

2015-07-01

Nanotechnology-based drug delivery systems can enhance drug permeation through the skin and improve the drug stability. The biodegradability and biocompatibility of cellulose nanocrystals have made these nanoparticles good candidates to use in biomedical applications. The hyperpigmentation is a common skin disorder that could be caused by number of reasons such as sun exposure and pregnancy. Hydroquinone could inhibit the production of melanin and eliminate the discolorations of skin. This study is aimed at introducing cellulose nanocrystals as suitable carriers for drug delivery to skin. Prepared cellulose nanocrystals were characterized by dynamic light scattering and atomic force microscopy. The size of cellulose nanocrystals determined using dynamic light scattering was 301 ± 10 nm. Hydroquinone-cellulose nanocrystal complex was prepared by incubating of hydroquinone solution in cellulose nanocrystals suspension. The size of hydroquinone-cellulose nanocrystal complex determined using dynamic light scattering was 310 ± 10 nm. The hydroquinone content of the hydroquinone-cellulose complex was determined using UV/vis spectroscopy. Hydroquinone was bound to cellulose nanocrystals representing 79.3 ± 2% maximum binding efficiency when 1.1 mg hydroquinone was added to 1 mL of cellulose nanocrystals suspension (2 mg cellulose nanocrystal). The hydroquinone-cellulose nanocrystal complex showed an approximately sustained release profile of hydroquinone. Approximately, 80% of bound hydroquinone released in 4 h. © 2014 John Wiley & Sons A/S.

Morphology evolution of single-crystalline hematite nanocrystals: magnetically recoverable nanocatalysts for enhanced facet-driven photoredox activity

NASA Astrophysics Data System (ADS)

Patra, Astam K.; Kundu, Sudipta K.; Bhaumik, Asim; Kim, Dukjoon

2015-12-01

We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity.We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06509g

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2010-04-13

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2005-03-08

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2015-06-23

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C; Alivisatos, A. Paul

2014-02-11

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, Paul A.

2015-11-10

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon [Pinole, CA; Schlamp, Michael C [Plainsboro, NJ; Alivisatos, A Paul [Oakland, CA

2011-09-27

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlam, Michael C; Alivisatos, A. Paul

2014-03-25

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2017-06-06

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Colloidal chemical synthesis and formation kinetics of uniformly sized nanocrystals of metals, oxides, and chalcogenides.

PubMed

Kwon, Soon Gu; Hyeon, Taeghwan

2008-12-01

Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized nanoparticles of copper and nickel using metal(II) acetylacetonates. Ni/Pd core/shell nanoparticles were synthesized by simply heating the reaction mixture composed of acetylacetonates of nickel and palladium. Using alternative chalcogen reagents, we synthesized uniform nanocrystals of various metal chalcogenides. Uniform nanocrystals of PbS, ZnS, CdS, and MnS were obtained by heating reaction mixtures composed of metal chlorides and sulfur dissolved in oleylamine. In the future, a detailed understanding of nanocrystal formation kinetics and synthetic chemistry will lead to the synthesis of uniform nanocrystals with controlled size, shape, and composition. In particular, the synthesis of uniform nanocrystals of doped materials, core/shell materials, and multicomponent materials is still a challenge. We expect that these uniformly sized nanocrystals will find important applications in areas including information technology, biomedicine, and energy/environmental technology.

Numerical model of a single nanocrystal devoted to the study of disordered nanocrystal floating gates of new flash memories

NASA Astrophysics Data System (ADS)

Leroy, Yann; Armeanu, Dumitru; Cordan, Anne-Sophie

2011-05-01

The improvement of our model concerning a single nanocrystal that belongs to a nanocrystal floating gate of a flash memory is presented. In order to extend the gate voltage range applicability of the model, the 3D continuum of states of either metallic or semiconducting electrodes is discretized into 2D subbands. Such an approach gives precise information about the mechanisms behind the charging or release processes of the nanocrystal. Then, the self-energy and screening effects of an electron within the nanocrystal are evaluated and introduced in the model. This enables a better determination of the operating point of the nanocrystal memory. The impact of those improvements on the charging or release time of the nanocrystal is discussed.

Semiconductor nanowhiskers: Synthesis, properties, and applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dubrovskii, V. G., E-mail: dubrovskii@mail.ioffe.ru; Cirlin, G. E., E-mail: Cirlin@beam.ioffe.ru; Ustinov, V. M., E-mail: Vmust@beam.ioffe.ru

2009-12-15

Recent results of studying the semiconductor's whisker nanocrystals are reviewed. Physical grounds of growing whisker nanocrystals using the mechanism vapor-liquid-crystal are given and the main epitaxial technologies of synthesis of whisker nanocrystals are described. Thermodynamic and kinetic factors controlling the morphological properties, composition, and crystal structure of whisker nanocrystals are considered in detail. The main theoretical models of the growth and structure of whisker nanocrystals are described. The data on physical properties of whisker nanocrystals and possibilities of their use in nanophotonics, nanoelectronics, and nanobiotechnology are presented.

Living Nanocrystals: Synthesis of Precisely Defined Metal Oxide Nanocrystals Through a Continuous Growth Process

NASA Astrophysics Data System (ADS)

Jansons, Adam Wayne

Colloidal nanocrystals offer new and improved performance in applications as well as less environmental impact when compared to traditional device fabrication methods. The important properties that enable improved applications are a direct result of nanocrystal structure. While there have been many great advances in the production of colloidal nanocrystals over the past three decades, precise, atomic-level control of the size, composition, and structure of the inorganic core remains challenging. Rather than dictate these material aspects through traditional synthetic routes, this dissertation details the development and exploitation of a colloidal nanocrystal synthetic method inspired by polymerization reactions. Living polymerization reactions offer precise control of polymer size and structure and have tremendously advanced polymer science, allowing the intuitive production of polymers and block co-polymers of well-defined molecular weights. Similarly, living nanocrystal synthetic methods allow an enhanced level of structural control, granting the synthesis of binary, doped, and core/shell nanocrystals of well-defined size, composition, and structure. This improved control in turn grants enhanced nanocrystal property performance and deepens our understanding of structure/property relationships. This dissertation defines living nanocrystal growth and demonstrates the potential of the living methods in the colloidal production of oxide nanocrystals. After a brief introduction, living growth is defined and discussed in the context of synthetic prerequisites, attributes, and outcomes. Living growth is also compared to more traditional colloidal nanocrystal synthetic methods. The following chapters then demonstrate the precise control living approaches offer in three separate studies; the first highlights sub-nanometer control of nanocrystal size from 2-22+ nm in diameter. Next the improvement in nanocrystal composition is illustrated using several transition metal dopants into an oxide nanocrystal matrix at near thermodynamically allowed compositions. Additionally, precise radial dopant placement is demonstrated, which has striking implications for material properties. The radial position of tin in tin-doped indium oxide nanocrystals and the resulting differences on the localized surface plasmon resonance are discussed. Finally, future opportunities are reviewed. This dissertation includes previously published co-authored material.

Synthesis and Doping of Silicon Nanocrystals for Versatile Nanocrystal Inks

NASA Astrophysics Data System (ADS)

Kramer, Nicolaas Johannes

The impact of nanotechnology on our society is getting larger every year. Electronics are becoming smaller and more powerful, the "Internet of Things" is all around us, and data generation is increasing exponentially. None of this would have been possible without the developments in nanotechnology. Crystalline semiconductor nanoparticles (nanocrystals) are one of the latest developments in the field of nanotechnology. This thesis addresses three important challenges for the transition of silicon nanocrystals from the lab bench to the marketplace: A better understanding of the nanocrystal synthesis was obtained, the electronic properties of the nanocrystals were characterized and tuned, and novel silicon nanocrystal inks were formed and applied using simple coating technologies. Plasma synthesis of nanocrystals has numerous advantages over traditional solution-based synthesis methods. While the formation of nanoparticles in low pressure nonthermal plasmas is well known, the heating mechanism leading to their crystallization is poorly understood. A combination of comprehensive plasma characterization with a nanoparticle heating model presented here reveals the underlying plasma physics leading to crystallization. The model predicts that the nanoparticles reach temperatures as high as 900 K in the plasma as a result of heating reactions on the nanoparticle surface. These temperatures are well above the gas temperature and sufficient for complete nanoparticle crystallization. Moving the field of plasma nanoparticle synthesis to atmospheric pressures is important for lowering its cost and making the process attractive for industrial applications. The heating and charging model for silicon nanoparticles was adapted in Chapter 3 to study plasmas maintained over a wide range of pressures (10 -- 105 Pa). The model considers three collisionality regimes and determines the dominant contribution of each regime under various plasma conditions. Strong nanoparticle cooling at atmospheric pressures necessitates high plasma densities to reach temperatures required for crystallization of nanoparticles. Using experimentally determined plasma properties from the literature, the model estimates the nanoparticle temperature that is achieved during synthesis at atmospheric pressures. It was found that temperatures well above those required for crystallization can be achieved. Now that the synthesis of nanocrystals is understood, the second half of this thesis will focus on doping of the nanocrystals. The doping of semiconductor nanocrystals, which is vital for the optimization of nanocrystal-based devices, remains a challenge. Gas phase plasma approaches have been very successful in incorporating dopant atoms into nanocrystals by simply adding a dopant precursor during synthesis. However, little is known about the electronic activation of these dopants. This was investigated with field-effect transistor measurements using doped silicon nanocrystal films. It was found that, analogous to bulk silicon, boron and phosphorous electronically dope silicon nanocrystals. However, the dopant activation efficiency remains low as a result of self-purification of the dopants to the nanocrystal surface. Next the plasmonic properties of heavily doped silicon nanocrystals was explored. While the synthesis method was identical, the plasmonic behavior of phosphorus-doped and boron-doped nanocrystals was found the be significantly different. Phosphorus-doped nanocrystals exhibit a plasmon resonance immediately after synthesis, while boron-doped nanocrystals require a post-synthesis annealing or oxidation treatment. This is a result of the difference in dopant location. Phosphorus is more likely to be incorporated into the core of the nanocrystal, while the majority of boron is placed on the surface of the nanocrystal. The oxidized boron-doped particles exhibit stable plasmonic properties, and therefore this allows for the production of air-stable silicon-based plasmonic materials which is very interesting for certain applications. Finally the boron atoms were used to form a Lewis acidic nanocrystal surface chemistry allowing for the creation of ligand-less silicon nanocrystal solutions. This represents an immense step towards an abundant, non-toxic alternative to Pb and Cd-based nanocrystal technologies. The lack of long ligand chains enables the production of dense films with excellent electrical conductivity. This was demonstrated by forming uniform nanocrystal thin-films using simple and inexpensive spray coating techniques.

Size-Dependent Melting Behavior of Colloidal In, Sn, and Bi Nanocrystals

PubMed Central

Liu, Minglu; Wang, Robert Y.

2015-01-01

Colloidal nanocrystals are a technologically important class of nanostructures whose phase change properties have been largely unexplored. Here we report on the melting behavior of In, Sn, and Bi nanocrystals dispersed in a polymer matrix. This polymer matrix prevents the nanocrystals from coalescing with one another and enables previously unaccessed observations on the melting behavior of colloidal nanocrystals. We measure the melting temperature, melting enthalpy, and melting entropy of colloidal nanocrystals with diameters of approximately 10 to 20 nm. All of these properties decrease as nanocrystal size decreases, although the depression rate for melting temperature is comparatively slower than that of melting enthalpy and melting entropy. We also observe an elevated melting temperature during the initial melt-freeze cycle that we attribute to surface stabilization from the organic ligands on the nanocrystal surface. Broad endothermic melting valleys and very large supercoolings in our calorimetry data suggest that colloidal nanocrystals exhibit a significant amount of surface pre-melting and low heterogeneous nucleation probabilities during freezing. PMID:26573146

Connecting the Particles in the Box - Controlled Fusion of Hexamer Nanocrystal Clusters within an AB6 Binary Nanocrystal Superlattice

PubMed Central

Treml, Benjamin E.; Lukose, Binit; Clancy, Paulette; Smilgies, Detlef-M; Hanrath, Tobias

2014-01-01

Binary nanocrystal superlattices present unique opportunities to create novel interconnected nanostructures by partial fusion of specific components of the superlattice. Here, we demonstrate the binary AB6 superlattice of PbSe and Fe2O3 nanocrystals as a model system to transform the central hexamer of PbSe nanocrystals into a single fused particle. We present detailed structural analysis of the superlattices by combining high-resolution X-ray scattering and electron microscopy. Molecular dynamics simulations show optimum separation of nanocrystals in agreement with the experiment and provide insights into the molecular configuration of surface ligands. We describe the concept of nanocrystal superlattices as a versatile ‘nanoreactor' to create and study novel materials based on precisely defined size, composition and structure of nanocrystals into a mesostructured cluster. We demonstrate ‘controlled fusion' of nanocrystals in the clusters in reactions initiated by thermal treatment and pulsed laser annealing. PMID:25339169

Enhanced luminescence of Cu-In-S nanocrystals by surface modification.

PubMed

Kim, Young-Kuk; Cho, Young-Sang; Chung, Kookchae; Choi, Chul-Jin; Shin, Pyung-Woo

2012-04-01

We have synthesized highly luminescent Cu-In-S nanocrystals by heating the mixture of metal carboxylates and alkylthiol under inert atmosphere. We modified the surface of CIS nanocrystals with zinc carboxylate and subsequent injection of alkylthiol. As a result of the surface modification, highly luminescent CIS@ZnS core/shell nanocrystals were synthesized. The luminescence quantum yield (QY) of best CIS@ZnS nanocrystals was above 50%, which is more than 10 times higher than the initial QY of CIS nanocrystals before surface modification (QY = 3%). Detailed study on the luminescence mechanism implies that etching of the surface of nanocrystals by dissociated carboxylate group (CH3COO-) and formation of epitaxial shell by Zn with sulfur from alkylthiol efficiently removed the surface defects which are major non-radiative recombination sites in semiconductor nanocrystals. In this study, we developed a novel surface modification route for monodispersed highly luminescent Cu-In-S nanocrystals with less toxic and highly stable precursors.

High-temperature crystallization of nanocrystals into three-dimensional superlattices

DOE PAGES

Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; ...

2017-07-31

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single-and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) ofmore » micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. In conclusion, the rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.« less

"A bridge over troubled gaps": up-conversion driven photocatalysis for hydrogen generation and pollutant degradation by near-infrared excitation.

PubMed

Acosta-Mora, P; Domen, K; Hisatomi, T; Lyu, H; Méndez-Ramos, J; Ruiz-Morales, J C; Khaidukov, N M

2018-02-15

Spectral up-conversion (UC) has been attracting growing interest for the effective harvesting of the near-infrared (NIR) part of sunlight for photocatalytic hydrogen production and environmental purification. We present evidence of NIR-to-UV-VIS photon conversion for degradation of organic dyes and hydrogen and oxygen evolution via water-splitting by TiO 2 and Rh-Cr oxide-loaded SrTiO 3 :Al photocatalysts, respectively.

White light upconversion emissions in Er3+/Tm3+/Yb3+ tridoped oxyfluoride glass

NASA Astrophysics Data System (ADS)

Guan, Xiaoping; Xu, Wei; Zhu, Shuang; Song, Qiutong; Wu, Xijun; Liu, Hailong

2015-10-01

Rare earth ions doped glasses producing visible upconversion emissions are of great interest due to their potential applications in the photonics filed. In fact, practical application of upconversion emissions has been used to obtain color image displays and white light sources. However, there are few reports on the thermal effect on tuning the emission color of the RE doped materials. In this work, the Er3+/Tm3+/Yb3+ tridoped oxyfluoride glasses were prepared through high temperature solid-state method. Under a 980 nm diode laser excitation, the upconversion emissions from the samples were studied. At room-temperature, bright white luminescence, whose CIE chromaticity coordinate was about (0.28, 0.31), can be obtained when the excitation power was 120 mW. The emission color was changed by varying the intensity ratios between RGB bands, which are strongly dependent on the rare earth ions concentration. The temperature dependent color emissions were also investigated. As temperature increased, the intensities for the emission bands presented different decay rates, finally resulting in the changing of the CIE coordinate. When the temperature was 573 K, white light with color coordinate of (0.31, 0.33) was achieved, which matches well with the white reference (0.33, 0.33). The color tunability, high quality of white light and intense emission intensity make the transparent oxyfluoride glasses excellent candidates for applications in solid-state lighting.

Energy transfer dynamics of Er3+/Nd3+ embedded SiO2-Al2O3-Na2CO3-SrF2-CaF2 glasses for optical communications

NASA Astrophysics Data System (ADS)

Gelija, Devarajulu; Kadathala, Linganna; Borelli, Deva Prasad Raju

2018-04-01

The fluorescence and upconversion studies of Er3+ doped and Er3+/Nd3+ co-doped silicate based oxyfluoride glasses have been systematically analyzed. The broad band NIR emissions (830-1700 nm), includes optical bands like O, E, S, C and L were observed in the Er3+-Nd3+ co-doped glasses. The NIR emission intensity peaks centered at 876, 1057, 1329 and 1534 nm were observed for the Er3+-Nd3+ co-doped glasses. In the co-doped samples the strongest emission intensity at 1534 nm increased up to 0.5 mol % and then decreased to 3.0 mol % of Nd3+ ions under the excitation of 980 nm. The upconversion studies of the co-doped samples were recorded under the excitation of 980 and 808 nm and found the upconversion emission peaks centered at 524, 530, 547, 590 and 656 nm. The energy transfer processes between the relevant excitation levels of Er3+ and Nd3+ ions and energy transfer efficiency were discussed. The obtained results indicate that Nd3+ can be an efficient sensitizer for Er3+ to enhance upconversion emission at green laser transition for sensors and NIR emission at 1534 nm for optical communication applications.

A pre-protective strategy for precise tumor targeting and efficient photodynamic therapy with a switchable DNA/upconversion nanocomposite.

PubMed

Yu, Zhengze; Ge, Yegang; Sun, Qiaoqiao; Pan, Wei; Wan, Xiuyan; Li, Na; Tang, Bo

2018-04-14

Tumor-specific targeting based on folic acid (FA) is one of the most common and significant approaches in cancer therapy. However, the expression of folate receptors (FRs) in normal tissues will lead to unexpected targeting and unsatisfactory therapeutic effect. To address this issue, we develop a pre-protective strategy for precise tumor targeting and efficient photodynamic therapy (PDT) using a switchable DNA/upconversion nanocomposite, which can be triggered in the acidic tumor microenvironment. The DNA/upconversion nanocomposite is composed of polyacrylic acid (PAA) coated upconversion nanoparticles (UCNPs), the surface of which is modified using FA and chlorin e6 (Ce6) functionalized DNA sequences with different lengths. Initially, FA on the shorter DNA was protected by a longer DNA to prevent the bonding to FRs on normal cells. Once reaching the acidic tumor microenvironment, C base-rich longer DNA forms a C-quadruplex, resulting in the exposure of the FA groups and the bonding of FA and FRs on cancer cell membranes to achieve precise targeting. Simultaneously, the photosensitizer chlorin e6 (Ce6) gets close to the surface of UCNPs, enabling the excitation of Ce6 to generate singlet oxygen ( 1 O 2 ) under near infrared light via Förster resonance energy transfer (FRET). In vivo experiments indicated that higher tumor targeting efficiency was achieved and the tumor growth was greatly inhibited through the pre-protective strategy.

Three-dimensional quick response code based on inkjet printing of upconversion fluorescent nanoparticles for drug anti-counterfeiting.

PubMed

You, Minli; Lin, Min; Wang, Shurui; Wang, Xuemin; Zhang, Ge; Hong, Yuan; Dong, Yuqing; Jin, Guorui; Xu, Feng

2016-05-21

Medicine counterfeiting is a serious issue worldwide, involving potentially devastating health repercussions. Advanced anti-counterfeit technology for drugs has therefore aroused intensive interest. However, existing anti-counterfeit technologies are associated with drawbacks such as the high cost, complex fabrication process, sophisticated operation and incapability in authenticating drug ingredients. In this contribution, we developed a smart phone recognition based upconversion fluorescent three-dimensional (3D) quick response (QR) code for tracking and anti-counterfeiting of drugs. We firstly formulated three colored inks incorporating upconversion nanoparticles with RGB (i.e., red, green and blue) emission colors. Using a modified inkjet printer, we printed a series of colors by precisely regulating the overlap of these three inks. Meanwhile, we developed a multilayer printing and splitting technology, which significantly increases the information storage capacity per unit area. As an example, we directly printed the upconversion fluorescent 3D QR code on the surface of drug capsules. The 3D QR code consisted of three different color layers with each layer encoded by information of different aspects of the drug. A smart phone APP was designed to decode the multicolor 3D QR code, providing the authenticity and related information of drugs. The developed technology possesses merits in terms of low cost, ease of operation, high throughput and high information capacity, thus holds great potential for drug anti-counterfeiting.

Monitoring Delamination of Thermal Barrier Coatings by Near-Infrared and Upconversion Luminescence Imaging

NASA Technical Reports Server (NTRS)

Eldridge, J. I.; Martin, R. E.; Singh, Jogender; Wolfe, Doug E.

2008-01-01

Previous work has demonstrated that TBC delamination can be monitored by incorporating a thin luminescent sublayer that produces greatly increased luminescence intensity from delaminated regions of the TBC. Initial efforts utilized visible-wavelength luminescence from either europium or erbium doped sublayers. This approach exhibited good sensitivity to delamination of electron-beam physical-vapor-deposited (EB-PVD) TBCs, but limited sensitivity to delamination of the more highly scattering plasma-sprayed TBCs due to stronger optical scattering and to interference by luminescence from rare-earth impurities. These difficulties have now been overcome by new strategies employing near-infrared (NIR) and upconversion luminescence imaging. NIR luminescence at 1550 nm was produced in an erbium plus ytterbium co-doped yttria-stabilized zirconia (YSZ) luminescent sublayer using 980-nm excitation. Compared to visible-wavelength luminescence, these NIR emission and excitation wavelengths are much more weakly scattered by the TBC and therefore show much improved depth-probing capabilities. In addition, two-photon upconversion luminescence excitation at 980 nm wavelength produces luminescence emission at 562 nm with near-zero fluorescence background and exceptional contrast for delamination indication. The ability to detect TBC delamination produced by Rockwell indentation and by furnace cycling is demonstrated for both EB-PVD and plasma-sprayed TBCs. The relative strengths of the NIR and upconversion luminescence methods for monitoring TBC delamination are discussed.

Enhanced near-infrared to visible upconversion nanoparticles of Ho³⁺-Yb³⁺-F⁻ tri-doped TiO₂ and its application in dye-sensitized solar cells with 37% improvement in power conversion efficiency.

PubMed

Yu, Jia; Yang, Yulin; Fan, Ruiqing; Liu, Danqing; Wei, Liguo; Chen, Shuo; Li, Liang; Yang, Bin; Cao, Wenwu

2014-08-04

New near-infrared (NIR)-to-green upconversion nanoparticles of Ho(3+)-Yb(3+)-F(-) tridoped TiO2 (UC-F-TiO2) were designed and fabricated via the hydrosol-hydrothermal method. Under 980 nm NIR excitation, UC-F-TiO2 emit strong green upconversion fluorescence with three emission bands at 543, 644, and 751 nm and convert the NIR light in situ to the dye-sensitive visible light that could effectively reduce the distance between upconversion materials and sensitizers; thus, they minimize the loss of the converted light. Our results show that this UC-F-TiO2 offers excellent opportunities for the other types of solar cells applications, such as organic solar cells, c-Si solar cells, multijunction solar cells, and so on. When integrating the UC-F-TiO2 into dye-sensitized solar cells (DSSCs), superior total energy conversion efficiency was achieved. Under AM1.5G light, open-circuit voltage reached 0.77 ± 0.01 V, short-circuit current density reached 21.00 ± 0.69 mA cm(-2), which resulted in an impressive overall energy conversion efficiency of 9.91 ± 0.30%, a 37% enhancement compared to DSSCs with pristine TiO2 photoanode.

Highly Efficient LiYF4:Yb(3+), Er(3+) Upconversion Single Crystal under Solar Cell Spectrum Excitation and Photovoltaic Application.

PubMed

Chen, Xu; Xu, Wen; Song, Hongwei; Chen, Cong; Xia, Haiping; Zhu, Yongsheng; Zhou, Donglei; Cui, Shaobo; Dai, Qilin; Zhang, Jiazhong

2016-04-13

Luminescent upconversion is a promising way to harvest near-infrared (NIR) sunlight and transforms it into visible light that can be directly absorbed by active materials of solar cells and improve their power conversion efficiency (PCE). However, it is still a great challenge to effectively improve the PCE of solar cells with the assistance of upconversion. In this work, we demonstrate the application of the transparent LiYF4:Yb(3+), Er(3+) single crystal as an independent luminescent upconverter to improve the PCE of perovskite solar cells. The LiYF4:Yb(3+), Er(3+) single crystal is prepared by an improved Bridgman method, and its internal quantum efficiency approached to 5.72% under 6.2 W cm(-2) 980 nm excitation. The power-dependent upconversion luminescence indicated that under the excitation of simulated sunlight the (4)F(9/2)-(4)I(15/2) red emission originally results from the cooperation of a 1540 nm photon and a 980 nm photon. Furthermore, when the single crystal is placed in front of the perovskite solar cells, the PCE is enhanced by 7.9% under the irradiation of simulated sunlight by 7-8 solar constants. This work implies the upconverter not only can serve as proof of principle for improving PCE of solar cells but also is helpful to practical application.

Smart Self-Assembled Nanosystem Based on Water-Soluble Pillararene and Rare-Earth-Doped Upconversion Nanoparticles for pH-Responsive Drug Delivery.

PubMed

Li, Haihong; Wei, Ruoyan; Yan, Gui-Hua; Sun, Ji; Li, Chunju; Wang, Haifang; Shi, Liyi; Capobianco, John A; Sun, Lining

2018-02-07

Exploring novel drug delivery systems with good stability and new structure to integrate pillararene and upconversion nanoparticles (UCNPs) into one system continues to be an important challenge. Herein, we report a novel preparation of a supramolecular upconversion nanosystem via the host-guest complexation based on carboxylate-based pillar[5]arene (WP5) and 15-carboxy-N,N,N-trialkylpentadecan-1-ammonium bromide (1)-functionalized UCNPs to produce WP5⊃1-UCNPs that can be loaded with the chemotherapeutic drug doxorubicin (DOX). Importantly, the WP5 on the surface of the drug-loaded nanosystem can be efficiently protonated under acidic conditions, resulting in the collapse of the nanosystem and drug release. Moreover, cellular uptake confirms that the nanosystem can enter human cervical cancer (HeLa) cells, resulting in drug accumulation in the cells. More importantly, cytotoxicity experiments demonstrated the excellent biocompatibility of WP5⊃1-UCNPs without loading DOX and that the nanosystem DOX-WP5⊃1-UCNPs exhibited an ability of killing HeLa cells effectively. We also investigated magnetic resonance imaging and upconversion luminescence imaging, which may be employed as visual imaging agents in cancer diagnosis and treatment. Thus, in the present work, we show a simple yet powerful strategy to combine UCNPs and pillar[5]arene to produce a unified nanosystem for dual-mode bioimaging-guided therapeutic applications.

Delivery and reveal of localization of upconversion luminescent microparticles and quantum dots in the skin in vivo by fractional laser microablation, multimodal imaging, and optical clearing

NASA Astrophysics Data System (ADS)

Volkova, Elena K.; Yanina, Irina Yu; Genina, Elina A.; Bashkatov, Alexey N.; Konyukhova, Julia G.; Popov, Alexey P.; Speranskaya, Elena S.; Bucharskaya, Alla B.; Navolokin, Nikita A.; Goryacheva, Irina Yu.; Kochubey, Vyacheslav I.; Sukhorukov, Gleb B.; Meglinski, Igor V.; Tuchin, Valery V.

2018-02-01

Delivery and spatial localization of upconversion luminescent microparticles [Y2O3:Yb, Er] (mean size ˜1.6 μm) and quantum dots (QDs) (CuInS2/ZnS nanoparticles coated with polyethylene glycol-based amphiphilic polymer, mean size ˜20 nm) inside rat skin was studied in vivo using a multimodal optical imaging approach. The particles were embedded into the skin dermis to the depth from 300 to 500 μm through microchannels performed by fractional laser microablation. Low-frequency ultrasound was applied to enhance penetration of the particles into the skin. Visualization of the particles was revealed using a combination of luminescent spectroscopy, optical coherence tomography, confocal microscopy, and histochemical analysis. Optical clearing was used to enhance the image contrast of the luminescent signal from the particles. It was demonstrated that the penetration depth of particles depends on their size, resulting in a different detection time interval (days) of the luminescent signal from microparticles and QDs inside the rat skin in vivo. We show that luminescent signal from the upconversion microparticles and QDs was detected after the particle delivery into the rat skin in vivo during eighth and fourth days, respectively. We hypothesize that the upconversion microparticles have created a long-time depot localized in the laser-created channels, as the QDs spread over the surrounding tissues.

Exceeding the solar cell Shockley-Queisser limit via thermal up-conversion of low-energy photons

NASA Astrophysics Data System (ADS)

Boriskina, Svetlana V.; Chen, Gang

2014-03-01

Maximum efficiency of ideal single-junction photovoltaic (PV) cells is limited to 33% (for 1 sun illumination) by intrinsic losses such as band edge thermalization, radiative recombination, and inability to absorb below-bandgap photons. This intrinsic thermodynamic limit, named after Shockley and Queisser (S-Q), can be exceeded by utilizing low-energy photons either via their electronic up-conversion or via the thermophotovoltaic (TPV) conversion process. However, electronic up-conversion systems have extremely low efficiencies, and practical temperature considerations limit the operation of TPV converters to the narrow-gap PV cells. Here we develop a conceptual design of a hybrid TPV platform, which exploits thermal up-conversion of low-energy photons and is compatible with conventional silicon PV cells by using spectral and directional selectivity of the up-converter. The hybrid platform offers sunlight-to-electricity conversion efficiency exceeding that imposed by the S-Q limit on the corresponding PV cells across a broad range of bandgap energies, under low optical concentration (1-300 suns), operating temperatures in the range 900-1700 K, and in simple flat panel designs. We demonstrate maximum conversion efficiency of 73% under illumination by non-concentrated sunlight. A detailed analysis of non-ideal hybrid platforms that allows for up to 15% of absorption/re-emission losses yields limiting efficiency value of 45% for Si PV cells.

Selective epitaxial growth of zinc blende-derivative on wurtzite-derivative: the case of polytypic Cu2CdSn(S1-xSex)4 nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Liang; Fan, Feng-Jia; Gong, Ming; Ge, Jin; Yu, Shu-Hong

2014-02-01

Polytypic nanocrystals with zinc blende (ZB) cores and wurtzite (WZ) arms, such as tetrapod and octopod nanocrystals, have been widely reported. However, polytypic nanocrystals with WZ cores and ZB arms or ends have been rarely reported. Here, we report a facile, solution-based approach to the synthesis of polytypic Cu2CdSn(S1-xSex)4 (CCTSSe) nanocrystals with ZB-derivative selectively engineered on (000+/-2)WZ facets of WZ-derived cores. Accordingly, two typical morphologies, i.e., bullet-like nanocrystals with a WZ-derivative core and one ZB-derivative end, and rugby ball-like nanocrystals with a WZ-derivative core and two ZB-derivative ends, can be selectively prepared. The epitaxial growth mechanism is confirmed by the time-dependent experiments. The ratio of rugby ball-like and bullet-like polytypic CCTSSe nanocrystals can be tuned through changing the amount of Cd precursor to adjust the reactivity difference between (0002)WZ and (000-2)WZ facets. These unique polytypic CCTSSe nanocrystals may find applications in energetic semiconducting materials for energy conversion in the future.Polytypic nanocrystals with zinc blende (ZB) cores and wurtzite (WZ) arms, such as tetrapod and octopod nanocrystals, have been widely reported. However, polytypic nanocrystals with WZ cores and ZB arms or ends have been rarely reported. Here, we report a facile, solution-based approach to the synthesis of polytypic Cu2CdSn(S1-xSex)4 (CCTSSe) nanocrystals with ZB-derivative selectively engineered on (000+/-2)WZ facets of WZ-derived cores. Accordingly, two typical morphologies, i.e., bullet-like nanocrystals with a WZ-derivative core and one ZB-derivative end, and rugby ball-like nanocrystals with a WZ-derivative core and two ZB-derivative ends, can be selectively prepared. The epitaxial growth mechanism is confirmed by the time-dependent experiments. The ratio of rugby ball-like and bullet-like polytypic CCTSSe nanocrystals can be tuned through changing the amount of Cd precursor to adjust the reactivity difference between (0002)WZ and (000-2)WZ facets. These unique polytypic CCTSSe nanocrystals may find applications in energetic semiconducting materials for energy conversion in the future. Electronic supplementary information (ESI) available: Detailed information about the polytypic CCTSSe nanocrystals syntheses, measurement and characterization, additional TEM and HRTEM images, PXRD analysis, EDS spectra and UV-vis-NIR spectra. See DOI: 10.1039/c3nr04948e.

Switchable Ni–Mn–Ga Heusler nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zayak, Alexey T.; Beckman, Scott P.; Tiago, Murilo L.

2008-10-02

Here, we examined bulk-like Heusler nanocrystals using real-space pseudopotentials constructed within density functional theory. The nanocrystals were made of various compositions of Ni-Mn-Ga in the size range from 15 up to 169 atoms. Among these compositions, the closest to the stoichiometric Ni 2MnGa were found to be the most stable. The Ni-based nanocrystals retained a tendency for tetragonal distortion, which is inherited from the bulk properties. Surface effects suppress the tetragonal structure in the smaller Ni-based nanocrystals, while bigger nanocrystals develop a bulk-like tetragonal distortion. We suggest the possibility of switchable Ni-Mn-Ga nanocrystals, which could be utilized for magnetic nano-shape-memorymore » applications.« less

Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.

Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

Charge Transport in Semiconductor Nanocrystal Solids

NASA Astrophysics Data System (ADS)

Talapin, Dmitri; Shevchenko, Elena; Lee, Jong Soo; Urban, Jeffrey; Mitzi, David; Murray, Christopher

2007-03-01

Self-assembly of chemically-synthesized nanocrystals can yield complex long-range ordered structures which can be used as model systems for studying transport phenomena in low-dimensional materials [1]. Treatment of close-packed PbSe nanocrystal arrays with hydrazine enhanced exchange coupling between the nanocrystals and improved conductance by more than ten orders of magnitude compared to native nanocrystal films [2]. The conductivity of PbSe nanocrystal solids can be switched between n- and p-type transports by controlling the saturation of electronic states at nanocrystal surfaces. Nanocrystal arrays form the n- and p-channels of field-effect transistors with electron and hole mobilities of 2.5 cm^2V-1s-1 and 0.3 cm^2V-1s-1, respectively, and current modulation Ion/Ioff˜10^3-10^4. The field-effect mobility in PbSe nanocrystal arrays is higher than the mobility of organic transistors while the easy switch between n- and p-transport allows realization of complimentary circuits and p-n junctions for nanocrystal-based solar cells and thermoelectric devices. [1] E. V. Shevchenko, D. V. Talapin, N. A. Kotov, S. O'Brien, C. B. Murray. Nature 439, 55 (2006). [2] D. V. Talapin, C. B. Murray. Science 310, 86 (2005).

Flexible and low-voltage integrated circuits constructed from high-performance nanocrystal transistors.

PubMed

Kim, David K; Lai, Yuming; Diroll, Benjamin T; Murray, Christopher B; Kagan, Cherie R

2012-01-01

Colloidal semiconductor nanocrystals are emerging as a new class of solution-processable materials for low-cost, flexible, thin-film electronics. Although these colloidal inks have been shown to form single, thin-film field-effect transistors with impressive characteristics, the use of multiple high-performance nanocrystal field-effect transistors in large-area integrated circuits has not been shown. This is needed to understand and demonstrate the applicability of these discrete nanocrystal field-effect transistors for advanced electronic technologies. Here we report solution-deposited nanocrystal integrated circuits, showing nanocrystal integrated circuit inverters, amplifiers and ring oscillators, constructed from high-performance, low-voltage, low-hysteresis CdSe nanocrystal field-effect transistors with electron mobilities of up to 22 cm(2) V(-1) s(-1), current modulation >10(6) and subthreshold swing of 0.28 V dec(-1). We fabricated the nanocrystal field-effect transistors and nanocrystal integrated circuits from colloidal inks on flexible plastic substrates and scaled the devices to operate at low voltages. We demonstrate that colloidal nanocrystal field-effect transistors can be used as building blocks to construct complex integrated circuits, promising a viable material for low-cost, flexible, large-area electronics.

Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Beberwyck, Brandon James

Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be made for its adoption as a routine synthetic approach.

Hydrothermal synthesis of tungsten doped tin dioxide nanocrystals

NASA Astrophysics Data System (ADS)

Zhou, Cailong; Li, Yufeng; Chen, Yiwen; Lin, Jing

2018-01-01

Tungsten doped tin dioxide (WTO) nanocrystals were synthesized through a one-step hydrothermal method. The structure, composition and morphology of WTO nanocrystals were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, UV-vis diffuse reflectance spectra, zeta potential analysis and high-resolution transmission electron microscopy. Results show that the as-prepared WTO nanocrystals were rutile-type structure with the size near 13 nm. Compared with the undoped tin dioxide nanocrystals, the WTO nanocrystals possessed better dispersity in ethanol phase and formed transparent sol.

Fabrication of all-inorganic nanocrystal solids through matrix encapsulation of nanocrystal arrays.

PubMed

Kinder, Erich; Moroz, Pavel; Diederich, Geoffrey; Johnson, Alexa; Kirsanova, Maria; Nemchinov, Alexander; O'Connor, Timothy; Roth, Dan; Zamkov, Mikhail

2011-12-21

A general strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films is reported. The present methodology goes beyond the traditional ligand-interlinking scheme and relies on encapsulation of morphologically defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles while rendering the nanocrystal film photoconductive. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells. © 2011 American Chemical Society

Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOEpatents

Weiss, Shimon; Bruchez, Jr., Marcel; Alivisatos, Paul

2006-09-05

A semiconductor nanocrystal compound is described capable of linking to an affinity molecule. The compound comprises (1) a semiconductor nanocrystal capable of emitting electromagnetic radiation and/or absorbing energy, and/or scattering or diffracting electromagnetic radiation--when excited by an electromagnetic radiation source or a particle beam; and (2) at least one linking agent, having a first portion linked to the semiconductor nanocrystal and a second portion capable of linking to an affinity molecule. The compound is linked to an affinity molecule to form a semiconductor nanocrystal probe capable of bonding with a detectable substance. subsequent exposure to excitation energy will excite the semiconductor nanocrystal in the probe causing the emission of electromagnetic radiation. Further described are processes for respectively: making the luminescent semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and using the probe to determine the presence of a detectable substance in a material.

Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOEpatents

Weiss, Shimon [Pinole, CA; Bruchez, Jr., Marcel; Alivisatos, Paul [Oakland, CA

2004-03-02

A semiconductor nanocrystal compound is described capable of linking to an affinity molecule. The compound comprises (1) a semiconductor nanocrystal capable of emitting electromagnetic radiation and/or absorbing energy, and/or scattering or diffracting electromagnetic radiation--when excited by an electromagnetic radiation source or a particle beam; and (2) at least one linking agent, having a first portion linked to the semiconductor nanocrystal and a second portion capable of linking to an affinity molecule. The compound is linked to an affinity molecule to form a semiconductor nanocrystal probe capable of bonding with a detectable substance. Subsequent exposure to excitation energy will excite the semiconductor nanocrystal in the probe, causing the emission of electromagnetic radiation. Further described are processes for respectively: making the semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and using the probe to determine the presence of a detectable substance in a material.

Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOEpatents

Weiss, Shimon; Bruchez, Jr., Marcel; Alivisatos, Paul

2005-08-09

A semiconductor nanocrystal compound is described capable of linking to an affinity molecule. The compound comprises (1) a semiconductor nanocrystal capable of emitting electromagnetic radiation and/or absorbing energy, and/or scattering or diffracting electromagnetic radiation--when excited by an electromagnetic radiation source or a particle beam; and (2) at least one linking agent, having a first portion linked to the semiconductor nanocrystal and a second portion capable of linking to an affinity molecule. The compound is linked to an affinity molecule to form a semiconductor nanocrystal probe capable of bonding with a detectable substance. Subsequent exposure to excitation energy will excite the semiconductor nanocrystal in the probe causing the emission of electromagnetic radiation. Further described are processes for respectively: making the luminescent semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and using the probe to determine the presence of a detectable substance in a material.

Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOEpatents

Weiss, Shimon; Bruchez, Jr., Marcel; Alivisatos, Paul

2002-01-01

A semiconductor nanocrystal compound is described capable of linking to an affinity molecule. The compound comprises (1) a semiconductor nanocrystal capable of emitting electromagnetic radiation and/or absorbing energy, and/or scattering or diffracting electromagnetic radiation--when excited by an electromagnetic radiation source or a particle beam; and (2) at least one linking agent, having a first portion linked to the semiconductor nanocrystal and a second portion capable of linking to an affity molecule. The compound is linked to an affinity molecule to form a semiconductor nanocrystal probe capable of bonding with a detectable substance. Subsequent exposure to excitation energy will excite the semiconductor nanocrystal in he probe, causing the emission of electromagnetic radiation. Further described are processes for respectively: making the semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and using the probe to determine the presence of a detectable substance in a material.

Novel green synthetic strategy to prepare ZnO nanocrystals using rambutan (Nephelium lappaceum L.) peel extract and its antibacterial applications.

PubMed

Yuvakkumar, R; Suresh, J; Nathanael, A Joseph; Sundrarajan, M; Hong, S I

2014-08-01

In the present investigation, we report a sustainable novel green synthetic strategy to synthesis zinc oxide nanocrystals. This is the first report on sustainable biosynthesis of zinc oxide nanocrystals employing Nephelium lappaceum L., peel extract as a natural ligation agent. Green synthesis of zinc oxide nanocrystals was carried out via zinc-ellagate complex formation using rambutan peel wastes. The successful formation of zinc oxide nanocrystals was confirmed employing standard characterisation studies. A possible mechanism for the formation of ZnO nanocrystals with rambutan peel extract was also proposed. The prepared ZnO nanocrystals were coated on the cotton fabric and their antibacterial activity were analyzed. ZnO nanocrystals coated cotton showed good antibacterial activity towards Escherichia coli (E. coli), gram negative bacteria and Staphylococcus aureus (S. aureus), gram positive bacteria. Copyright © 2014 Elsevier B.V. All rights reserved.

Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus.

PubMed

Kramer, Nicolaas J; Schramke, Katelyn S; Kortshagen, Uwe R

2015-08-12

Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicon's low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year.

Stoichiometric control of lead chalcogenide nanocrystal solids to enhance their electronic and optoelectronic device performance.

PubMed

Oh, Soong Ju; Berry, Nathaniel E; Choi, Ji-Hyuk; Gaulding, E Ashley; Paik, Taejong; Hong, Sung-Hoon; Murray, Christopher B; Kagan, Cherie R

2013-03-26

We investigate the effects of stoichiometric imbalance on the electronic properties of lead chalcogenide nanocrystal films by introducing excess lead (Pb) or selenium (Se) through thermal evaporation. Hall-effect and capacitance-voltage measurements show that the carrier type, concentration, and Fermi level in nanocrystal solids may be precisely controlled through their stoichiometry. By manipulating only the stoichiometry of the nanocrystal solids, we engineer the characteristics of electronic and optoelectronic devices. Lead chalcogenide nanocrystal field-effect transistors (FETs) are fabricated at room temperature to form ambipolar, unipolar n-type, and unipolar p-type semiconducting channels as-prepared and with excess Pb and Se, respectively. Introducing excess Pb forms nanocrystal FETs with electron mobilities of 10 cm(2)/(V s), which is an order of magnitude higher than previously reported in lead chalcogenide nanocrystal devices. Adding excess Se to semiconductor nanocrystal solids in PbSe Schottky solar cells enhances the power conversion efficiency.

Enhanced oral bioavailability of glycyrrhetinic acid via nanocrystal formulation.

PubMed

Lei, Yaya; Kong, Yindi; Sui, Hong; Feng, Jun; Zhu, Rongyue; Wang, Wenping

2016-10-01

The purpose of this study was to prepare solid nanocrystals of glycyrrhetinic acid (GA) for improved oral bioavailability. The anti-solvent precipitation-ultrasonication method followed by freeze-drying was adopted for the preparation of GA nanocrystals. The physicochemical properties, drug dissolution and pharmacokinetic of the obtained nanocrystals were investigated. GA nanocrystals showed a mean particle size of 220 nm and shaped like short rods. The analysis results from differential scanning calorimetry and X-ray powder diffraction indicated that GA remained in crystalline state despite a huge size reduction. The equilibrium solubility and dissolution rate of GA nanocrystal were significantly improved in comparison with those of the coarse GA or the physical mixture. The bioavailability of GA nanocrystals in rats was 4.3-fold higher than that of the coarse GA after oral administration. With its rapid dissolution and absorption performance, the solid nanocrystal might be a more preferable formulation for oral administration of poorly soluble GA.

Si nanocrystals-based multilayers for luminescent and photovoltaic device applications

NASA Astrophysics Data System (ADS)

Lu, Peng; Li, Dongke; Cao, Yunqing; Xu, Jun; Chen, Kunji

2018-06-01

Low dimensional Si materials have attracted much attention because they can be developed in many kinds of new-generation nano-electronic and optoelectronic devices, among which Si nanocrystals-based multilayered material is one of the most promising candidates and has been extensively studied. By using multilayered structures, the size and distribution of nanocrystals as well as the barrier thickness between two adjacent Si nanocrystal layers can be well controlled, which is beneficial to the device applications. This paper presents an overview of the fabrication and device applications of Si nanocrystals, especially in luminescent and photovoltaic devices. We first introduce the fabrication methods of Si nanocrystals-based multilayers. Then, we systematically review the utilization of Si nanocrystals in luminescent and photovoltaic devices. Finally, some expectations for further development of the Si nanocrystals-based photonic and photovoltaic devices are proposed. Project supported by the National Natural Science Foundation of China (Nos. 11774155, 11274155).

Semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOEpatents

Weiss, Shimon; Bruchez, Marcel; Alivisatos, Paul

2014-01-28

A semiconductor nanocrystal compound and probe are described. The compound is capable of linking to one or more affinity molecules. The compound comprises (1) one or more semiconductor nanocrystals capable of, in response to exposure to a first energy, providing a second energy, and (2) one or more linking agents, having a first portion linked to the one or more semiconductor nanocrystals and a second portion capable of linking to one or more affinity molecules. One or more semiconductor nanocrystal compounds are linked to one or more affinity molecules to form a semiconductor nanocrystal probe capable of bonding with one or more detectable substances in a material being analyzed, and capable of, in response to exposure to a first energy, providing a second energy. Also described are processes for respectively: making the semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and treating materials with the probe.

Semiconductor nanocrystal probes for biological applications and process for making and using such probes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weiss, Shimon; Bruchez, Marcel; Alivisatos, Paul A.

2016-12-27

A semiconductor nanocrystal compound and probe are described. The compound is capable of linking to one or more affinity molecules. The compound comprises (1) one or more semiconductor nanocrystals capable of, in response to exposure to a first energy, providing a second energy, and (2) one or more linking agents, having a first portion linked to the one or more semiconductor nanocrystals and a second portion capable of linking to one or more affinity molecules. One or more semiconductor nanocrystal compounds are linked to one or more affinity molecules to form a semiconductor nanocrystal probe capable of bonding with onemore » or more detectable substances in a material being analyzed, and capable of, in response to exposure to a first energy, providing a second energy. Also described are processes for respectively: making the semiconductor nanocrystal compound; making the semiconductor nanocrystal probe; and treating materials with the probe.« less

Enhanced performance of dye-sensitized solar cells based on TiO{sub 2} with NIR-absorption and visible upconversion luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Li; Yulin, Yang, E-mail: ylyang@hit.edu.cn; Mi, Zhou

2013-02-15

TiO{sub 2} with NIR-absorption and visible upconversion luminescence (UC-TiO{sub 2}) is prepared by a sol-gel method and calcined at 700 Degree-Sign C for 6 h. The material broadens the response region of dye sensitized solar cells (DSSCs) from an ultraviolet-visible region to the whole region of the solar spectrum. It shifts NIR sunlight to visible light which matches the strong absorbing region of the dye (N719). DSSCs based on UC-TiO{sub 2} achieved higher conversion efficiency than that on raw TiO{sub 2}. UC-TiO{sub 2} was mixed with commercial raw TiO{sub 2} as additive, and the short-circuit current density, open-circuit voltage andmore » conversion efficiency of the DSSC reached to the optimum values 13.38 mA/cm{sup 2}, 0.78 V and 6.63% (AM1.5 global), comparing with the blank values: 7.99 mA/cm{sup 2}, 0.75 V and 4.07%, respectively. Also the mechanisms of upconversion by multiphoton absorption and energy transfer processes are interpreted in this paper. - Graphical abstract: By introducing TiO{sub 2} with NIR-absorption and visible up-conversion luminescence into DSSC, a signal reflection was explored from ultra-violet region to visible region, and to near-IR region. Highlights: Black-Right-Pointing-Pointer TiO{sub 2} with NIR-absorption and visible up-conversion luminescence (UC-TiO{sub 2}) was prepared by a sol-gel method. Black-Right-Pointing-Pointer A systematic characterization and analysis was carried out to discuss the mechanism. Black-Right-Pointing-Pointer A significantly enhanced performance of DSSC was explored by using UC-TiO{sub 2} as an additive.« less

Ho3+-Yb3+ codoped tellurite based glasses in visible lasers and optical devices: Judd-Ofelt analysis and frequency upconversion

NASA Astrophysics Data System (ADS)

Azam, Mohd; Rai, Vineet Kumar

2017-04-01

The optical absorption and frequency upconversion emission in the Ho3+/Yb3+ codoped TeO2-ZnO (TZ), TeO2-ZnO-WO3 (TZW) and TeO2-ZnO-WO3-TiO2 (TZWTi) glasses prepared by melting and quenching method has been studied. Judd-Ofelt theory has been used to calculate the Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6), transition probabilities, radiative lifetimes, absorption cross sections and the branching ratios. Upconversion (UC) emission bands centered at ∼ 549 nm, ∼658 nm and ∼754 nm are observed upon 980 nm excitation. On codoping with the Yb3+ ions at 3.0 mol% the upconversion emission intensity enhancement of about ∼57 times, ∼342 times and ∼480 times for the green band whereas for the red band arising from the Ho3+ ions it is about ∼71 times, ∼438 times and ∼707 times respectively have been observed. The enhancement observed in the UC emission intensity is explained on the basis of efficient energy transfer from Yb3+ to Ho3+, larger absorption cross section, larger oscillator strengths and increase in the local field corrections factor. The spectroscopic quality factor Ω4/Ω6 has been calculated to get the information about the developed materials for laser applications. The upconversion emission cross section determined on the basis of Judd-Ofelt analysis is found to be maximum for Ho-Yb-TZWTi glass. The nephelauxetic ratio, bonding and covalency parameters have been calculated to know the nature of bonding between the rare earth ions and neighbouring oxygen atoms. The high color purity 83.8% has been reported in the codoped glasses at ∼81.2 W/cm2 pump power density.

TiO2 -coated fluoride nanoparticles for dental multimodal optical imaging.

PubMed

Braz, Ana K S; Moura, Diógenes S; Gomes, Anderson S L; Ohulchanskyy, Tymish Y; Chen, Guanying; Liu, Maixian; Damasco, Jossana; de Araujo, Renato E; Prasad, Paras N

2018-04-01

Core-shell nanostructures associated with photonics techniques have found innumerous applications in diagnostics and therapy. In this work, we introduce a novel core-shell nanostructure design that serves as a multimodal optical imaging contrast agent for dental adhesion evaluation. This nanostructure consists of a rare-earth-doped (NaYF 4 :Yb 60%, Tm 0.5%)/NaYF 4 particle as the core (hexagonal prism, ~51 nm base side length) and the highly refractive TiO 2 material as the shell (~thickness of 15 nm). We show that the TiO 2 shell provides enhanced contrast for optical coherence tomography (OCT), while the rare-earth-doped core upconverts excitation light from 975 nm to an emission peaked at 800 nm for photoluminescence imaging. The OCT and the photoluminescence wide-field images of human tooth were demonstrated with this nanoparticle core-shell contrast agent. In addition, the described core-shell nanoparticles (CSNps) were dispersed in the primer of a commercially available dental bonding system, allowing clear identification of dental adhesive layers with OCT. We evaluated that the presence of the CSNp in the adhesive induced an enhancement of 67% scattering coefficient to significantly increase the OCT contrast. Moreover, our results highlight that the upconversion photoluminescence in the near-infrared spectrum region is suitable for image of deep dental tissue. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potentiometric Titrations for Measuring the Capacitance of Colloidal Photodoped ZnO Nanocrystals.

PubMed

Brozek, Carl K; Hartstein, Kimberly H; Gamelin, Daniel R

2016-08-24

Colloidal semiconductor nanocrystals offer a unique opportunity to bridge molecular and bulk semiconductor redox phenomena. Here, potentiometric titration is demonstrated as a method for quantifying the Fermi levels and charging potentials of free-standing colloidal n-type ZnO nanocrystals possessing between 0 and 20 conduction-band electrons per nanocrystal, corresponding to carrier densities between 0 and 1.2 × 10(20) cm(-3). Potentiometric titration of colloidal semiconductor nanocrystals has not been described previously, and little precedent exists for analogous potentiometric titration of any soluble reductants involving so many electrons. Linear changes in Fermi level vs charge-carrier density are observed for each ensemble of nanocrystals, with slopes that depend on the nanocrystal size. Analysis indicates that the ensemble nanocrystal capacitance is governed by classical surface electrical double layers, showing no evidence of quantum contributions. Systematic shifts in the Fermi level are also observed with specific changes in the identity of the charge-compensating countercation. As a simple and contactless alternative to more common thin-film-based voltammetric techniques, potentiometric titration offers a powerful new approach for quantifying the redox properties of colloidal semiconductor nanocrystals.

The surface structure of silver-coated gold nanocrystals and its influence on shape control

DOE PAGES

Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; ...

2015-07-08

Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A uniquemore » approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.« less

Improving polymer/nanocrystal hybrid solar cell performance via tuning ligand orientation at CdSe quantum dot surface.

PubMed

Fu, Weifei; Wang, Ling; Zhang, Yanfang; Ma, Ruisong; Zuo, Lijian; Mai, Jiangquan; Lau, Tsz-Ki; Du, Shixuan; Lu, Xinhui; Shi, Minmin; Li, Hanying; Chen, Hongzheng

2014-11-12

Achieving superior solar cell performance based on the colloidal nanocrystals remains challenging due to their complex surface composition. Much attention has been devoted to the development of effective surface modification strategies to enhance electronic coupling between the nanocrystals to promote charge carrier transport. Herein, we aim to attach benzenedithiol ligands onto the surface of CdSe nanocrystals in the "face-on" geometry to minimize the nanocrystal-nanocrystal or polymer-nanocrystal distance. Furthermore, the "electroactive" π-orbitals of the benzenedithiol are expected to further enhance the electronic coupling, which facilitates charge carrier dissociation and transport. The electron mobility of CdSe QD films was improved 20 times by tuning the ligand orientation, and high performance poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT):CdSe nanocrystal hybrid solar cells were also achieved, showing a highest power conversion efficiency of 4.18%. This research could open up a new pathway to improve further the performance of colloidal nanocrystal based solar cells.

Synthesis of ligand-stabilized metal oxide nanocrystals and epitaxial core/shell nanocrystals via a lower-temperature esterification process.

PubMed

Ito, Daisuke; Yokoyama, Shun; Zaikova, Tatiana; Masuko, Keiichiro; Hutchison, James E

2014-01-28

The properties of metal oxide nanocrystals can be tuned by incorporating mixtures of matrix metal elements, adding metal ion dopants, or constructing core/shell structures. However, high-temperature conditions required to synthesize these nanocrystals make it difficult to achieve the desired compositions, doping levels, and structural control. We present a lower temperature synthesis of ligand-stabilized metal oxide nanocrystals that produces crystalline, monodisperse nanocrystals at temperatures well below the thermal decomposition point of the precursors. Slow injection (0.2 mL/min) of an oleic acid solution of the metal oleate complex into an oleyl alcohol solvent at 230 °C results in a rapid esterification reaction and the production of metal oxide nanocrystals. The approach produces high yields of crystalline, monodisperse metal oxide nanoparticles containing manganese, iron, cobalt, zinc, and indium within 20 min. Synthesis of tin-doped indium oxide (ITO) can be accomplished with good control of the tin doping levels. Finally, the method makes it possible to perform epitaxial growth of shells onto nanocrystal cores to produce core/shell nanocrystals.

Ce3+-doped LaF3 nanoparticles: Wet-chemical synthesis and photo-physical characteristics "optical properties of LaF3:Ce nanomaterials"

NASA Astrophysics Data System (ADS)

Tabatabaee, F.; Sabbagh Alvani, A. A.; Sameie, H.; Moosakhani, S.; Salimi, R.; Taherian, M.

2014-01-01

The most effective process parameters were determined to synthesize spherical LaF3 nanoparticles with controllable size based on ethylenediaminetetraacetic acid (EDTA) via co-precipitation technique. Thermogravimetricdifferential thermal analysis, X-ray diffraction, scanning electron microscopy, dynamic light scattering and FT-IR spectroscopy were used to characterize the resulting powders. Detailed investigations revealed that the optimal LaF3 host nano-material was obtained when NH4F was used as a fluoride source in the presence of EDTA at pH = 5. Furthermore, photoluminescence spectra showed an intense double emission peak at 289 and 302 nm for cerium-doped LaF3 nanocrystals excited at 253 nm, which was assigned to the well-known 5d→4f (2F5/2 and 2F7/2) transitions of Ce3+ levels due to luminescence center mechanism. The experimental results indicate that the synthesized LaF3:0.05Ce powders with a band gap of 5.3 eV are promising phosphors for high density scintillators.

Blue-green upconversion laser

DOEpatents

Nguyen, D.C.; Faulkner, G.E.

1990-08-14

A blue-green laser (450--550 nm) uses a host crystal doped with Tm[sup 3+]. The Tm[sup 3+] is excited through upconversion by a red pumping laser and an IR pumping laser to a state which transitions to a relatively lower energy level through emissions in the blue-green band, e.g., 450.20 nm at 75 K. The exciting laser may be tunable dye lasers or may be solid-state semiconductor laser, e.g., GaAlAs and InGaAlP. 3 figs.

Blue-green upconversion laser

DOEpatents

Nguyen, Dinh C.; Faulkner, George E.

1990-01-01

A blue-green laser (450-550 nm) uses a host crystal doped with Tm.sup.3+. The Tm.sup.+ is excited through upconversion by a red pumping laser and an IR pumping laser to a state which transitions to a relatively lower energy level through emissions in the blue-green band, e.g., 450.20 nm at 75 K. The exciting laser may be tunable dye lasers or may be solid-state semiconductor laser, e.g., GaAlAs and InGaAlP.

Dental optical tomography with upconversion nanoparticles—a feasibility study

PubMed Central

Long, Feixiao; Intes, Xavier

2017-01-01

Abstract. Upconversion nanoparticles (UCNPs) have the unique ability to emit multiple colors upon excitation by near-infrared (NIR) light. Herein, we investigate the potential use of UCNPs as contrast agents for dental optical tomography, with a focus on monitoring the status of fillings after dental restoration. The potential of performing tomographic imaging using UCNP emission of visible or NIR light is established. This in silico and ex vivo study paves the way toward employing UCNPs as theranostic agents for dental applications. PMID:28586852

Dental optical tomography with upconversion nanoparticles—a feasibility study

NASA Astrophysics Data System (ADS)

Long, Feixiao; Intes, Xavier

2017-06-01

Upconversion nanoparticles (UCNPs) have the unique ability to emit multiple colors upon excitation by near-infrared (NIR) light. Herein, we investigate the potential use of UCNPs as contrast agents for dental optical tomography, with a focus on monitoring the status of fillings after dental restoration. The potential of performing tomographic imaging using UCNP emission of visible or NIR light is established. This in silico and ex vivo study paves the way toward employing UCNPs as theranostic agents for dental applications.

Dental optical tomography with upconversion nanoparticles-a feasibility study.

PubMed

Long, Feixiao; Intes, Xavier

2017-06-01

Upconversion nanoparticles (UCNPs) have the unique ability to emit multiple colors upon excitation by near-infrared (NIR) light. Herein, we investigate the potential use of UCNPs as contrast agents for dental optical tomography, with a focus on monitoring the status of fillings after dental restoration. The potential of performing tomographic imaging using UCNP emission of visible or NIR light is established. This in silico and ex vivo study paves the way toward employing UCNPs as theranostic agents for dental applications.

Integrated four-channel all-fiber up-conversion single-photon-detector with adjustable efficiency and dark count.

PubMed

Zheng, Ming-Yang; Shentu, Guo-Liang; Ma, Fei; Zhou, Fei; Zhang, Hai-Ting; Dai, Yun-Qi; Xie, Xiuping; Zhang, Qiang; Pan, Jian-Wei

2016-09-01

Up-conversion single photon detector (UCSPD) has been widely used in many research fields including quantum key distribution, lidar, optical time domain reflectrometry, and deep space communication. For the first time in laboratory, we have developed an integrated four-channel all-fiber UCSPD which can work in both free-running and gate modes. This compact module can satisfy different experimental demands with adjustable detection efficiency and dark count. We have characterized the key parameters of the UCSPD system.

Cellular internalization of LiNbO3 nanocrystals for second harmonic imaging and the effects on stem cell differentiation

NASA Astrophysics Data System (ADS)

Li, Jianhua; Qiu, Jichuan; Guo, Weibo; Wang, Shu; Ma, Baojin; Mou, Xiaoning; Tanes, Michael; Jiang, Huaidong; Liu, Hong

2016-03-01

Second harmonic generation (SHG) nanocrystals have recently been reported to label cancer cells and other functional cell lines due to their unique double-frequency property. In this paper, we report for the first time the use of lithium niobate (LiNbO3, LN) nanocrystals as SHG labels for imaging stem cells. Rat mesenchymal stem cells (rMSCs) were labeled with LN nanocrystals in order to study the cellular internalization of the nanocrystals and the influence on stem cell differentiation. The results showed that LN nanocrystals were endocytosed by the rMSCs and the distribution of the internalized nanoparticles demonstrated a high consistency with the orientation of the actin filaments. Besides, LN-labeled rMSCs showed a concentration-dependent viability. Most importantly, rMSCs labeled with 50 μg per mL of LN nanocrystals retained their ability to differentiate into both osteogenic and adipogenic lineages. The results prove that LN nanocrystals can be used as a cytocompatible, near-infrared (NIR) light driven cell label for long-term imaging, without hindering stem cell differentiation. This work will promote the use of LN nanocrystals to broader applications like deep-tissue tracking, remote drug delivery and stem cell therapy.Second harmonic generation (SHG) nanocrystals have recently been reported to label cancer cells and other functional cell lines due to their unique double-frequency property. In this paper, we report for the first time the use of lithium niobate (LiNbO3, LN) nanocrystals as SHG labels for imaging stem cells. Rat mesenchymal stem cells (rMSCs) were labeled with LN nanocrystals in order to study the cellular internalization of the nanocrystals and the influence on stem cell differentiation. The results showed that LN nanocrystals were endocytosed by the rMSCs and the distribution of the internalized nanoparticles demonstrated a high consistency with the orientation of the actin filaments. Besides, LN-labeled rMSCs showed a concentration-dependent viability. Most importantly, rMSCs labeled with 50 μg per mL of LN nanocrystals retained their ability to differentiate into both osteogenic and adipogenic lineages. The results prove that LN nanocrystals can be used as a cytocompatible, near-infrared (NIR) light driven cell label for long-term imaging, without hindering stem cell differentiation. This work will promote the use of LN nanocrystals to broader applications like deep-tissue tracking, remote drug delivery and stem cell therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00785f

Semiconductor nanocrystal-based phagokinetic tracking

DOEpatents

Alivisatos, A Paul; Larabell, Carolyn A; Parak, Wolfgang J; Le Gros, Mark; Boudreau, Rosanne

2014-11-18

Methods for determining metabolic properties of living cells through the uptake of semiconductor nanocrystals by cells. Generally the methods require a layer of neutral or hydrophilic semiconductor nanocrystals and a layer of cells seeded onto a culture surface and changes in the layer of semiconductor nanocrystals are detected. The observed changes made to the layer of semiconductor nanocrystals can be correlated to such metabolic properties as metastatic potential, cell motility or migration.

Intrinsic behavior of face-centered-cubic supra-crystals of nanocrystals self-organized on mesoscopic scale

NASA Astrophysics Data System (ADS)

Pileni, M. P.

2005-12-01

We describe intrinsic behavior due to the high ordering of nanocrystals at the mesoscopic scale. The first example shows well-defined columns in the formation of cobalt nanocrystals when an applied magnetic field is applied during the evaporation process. Collective breathing properties between nanocrystals are demonstrated. In both cases, these features are observed when the nanocrystals are highly ordered in fcc supra-crystals.

Nanocrystal thin film fabrication methods and apparatus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kagan, Cherie R.; Kim, David K.; Choi, Ji-Hyuk

Nanocrystal thin film devices and methods for fabricating nanocrystal thin film devices are disclosed. The nanocrystal thin films are diffused with a dopant such as Indium, Potassium, Tin, etc. to reduce surface states. The thin film devices may be exposed to air during a portion of the fabrication. This enables fabrication of nanocrystal-based devices using a wider range of techniques such as photolithography and photolithographic patterning in an air environment.

Infrared emitting and photoconducting colloidal silver chalcogenide nanocrystal quantum dots from a silylamide-promoted synthesis.

PubMed

Yarema, Maksym; Pichler, Stefan; Sytnyk, Mykhailo; Seyrkammer, Robert; Lechner, Rainer T; Fritz-Popovski, Gerhard; Jarzab, Dorota; Szendrei, Krisztina; Resel, Roland; Korovyanko, Oleksandra; Loi, Maria Antonietta; Paris, Oskar; Hesser, Günter; Heiss, Wolfgang

2011-05-24

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.

One-step DNA-programmed growth of luminescent and biofunctionalized nanocrystals

NASA Astrophysics Data System (ADS)

Ma, Nan; Sargent, Edward H.; Kelley, Shana O.

2009-02-01

Colloidal semiconductor nanocrystals are widely used as lumiphores in biological imaging because their luminescence is both strong and stable, and because they can be biofunctionalized. During synthesis, nanocrystals are typically passivated with hydrophobic organic ligands, so it is then necessary either to replace these ligands or encapsulate the nanocrystals with hydrophilic moieties to make the lumiphores soluble in water. Finally, biological labels must be added to allow the detection of nucleic acids, proteins and specific cell types. This multistep process is time- and labour-intensive and thus out of reach of many researchers who want to use luminescent nanocrystals as customized lumiphores. Here, we show that a single designer ligand-a chimeric DNA molecule-can controllably program both the growth and the biofunctionalization of the nanocrystals. One part of the DNA sequence controls the nanocrystal passivation and serves as a ligand, while another part controls the biorecognition. The synthetic protocol reported here is straightforward and produces a homogeneous dispersion of nanocrystal lumiphores functionalized with a single biomolecular receptor. The nanocrystals exhibit strong optical emission in the visible region, minimal toxicity and have hydrodynamic diameters of ~6 nm, which makes them suitable for bioimaging. We show that the nanocrystals can specifically bind DNA, proteins or cells that have unique surface recognition markers.

Detection of early primary colorectal cancer with upconversion luminescent NP-based molecular probes

NASA Astrophysics Data System (ADS)

Liu, Chunyan; Qi, Yifei; Qiao, Ruirui; Hou, Yi; Chan, Kaying; Li, Ziqian; Huang, Jiayi; Jing, Lihong; Du, Jun; Gao, Mingyuan

2016-06-01

Early detection and diagnosis of cancers is extremely beneficial for improving the survival rate of cancer patients and molecular imaging techniques are believed to be relevant for offering clinical solutions. Towards early cancer detection, we developed a primary animal colorectal cancer model and constructed a tumor-specific imaging probe by using biocompatible NaGdF4:Yb,Er@NaGdF4 upconversion luminescent NPs for establishing a sensitive early tumor imaging method. The primary animal tumor model, which can better mimic the human colorectal cancer, was built upon continual administration of 1,2-dimethylhydrazine in Kunming mice and the tumor development was carefully monitored through histopathological and immunohistochemical analyses to reveal the pathophysiological processes and molecular features of the cancer microenvironment. The upconversion imaging probe was constructed through covalent coupling of PEGylated core-shell NPs with folic acid whose receptor is highly expressed in the primary tumors. Upon 980 nm laser excitation, the primary colorectal tumors in the complex abdominal environment were sensitively imaged owing to the ultralow background of the upconversion luminescence and the high tumor-targeting specificity of the nanoprobe. We believe that the current studies provide a highly effective and potential approach for early colorectal cancer diagnosis and tumor surgical navigation.Early detection and diagnosis of cancers is extremely beneficial for improving the survival rate of cancer patients and molecular imaging techniques are believed to be relevant for offering clinical solutions. Towards early cancer detection, we developed a primary animal colorectal cancer model and constructed a tumor-specific imaging probe by using biocompatible NaGdF4:Yb,Er@NaGdF4 upconversion luminescent NPs for establishing a sensitive early tumor imaging method. The primary animal tumor model, which can better mimic the human colorectal cancer, was built upon continual administration of 1,2-dimethylhydrazine in Kunming mice and the tumor development was carefully monitored through histopathological and immunohistochemical analyses to reveal the pathophysiological processes and molecular features of the cancer microenvironment. The upconversion imaging probe was constructed through covalent coupling of PEGylated core-shell NPs with folic acid whose receptor is highly expressed in the primary tumors. Upon 980 nm laser excitation, the primary colorectal tumors in the complex abdominal environment were sensitively imaged owing to the ultralow background of the upconversion luminescence and the high tumor-targeting specificity of the nanoprobe. We believe that the current studies provide a highly effective and potential approach for early colorectal cancer diagnosis and tumor surgical navigation. Electronic supplementary information (ESI) available: (1) Molecular structure of Jeffamine-modified FA; (2) immunohistochemical analysis of FR expression in the colorectal tissue derived from mice treated with NaCl at different weeks; (3) biodistributions of probes of NP-FA and NP-IgG in the main organs of mice. See DOI: 10.1039/c5nr07858j

Three-dimensional quick response code based on inkjet printing of upconversion fluorescent nanoparticles for drug anti-counterfeiting

NASA Astrophysics Data System (ADS)

You, Minli; Lin, Min; Wang, Shurui; Wang, Xuemin; Zhang, Ge; Hong, Yuan; Dong, Yuqing; Jin, Guorui; Xu, Feng

2016-05-01

Medicine counterfeiting is a serious issue worldwide, involving potentially devastating health repercussions. Advanced anti-counterfeit technology for drugs has therefore aroused intensive interest. However, existing anti-counterfeit technologies are associated with drawbacks such as the high cost, complex fabrication process, sophisticated operation and incapability in authenticating drug ingredients. In this contribution, we developed a smart phone recognition based upconversion fluorescent three-dimensional (3D) quick response (QR) code for tracking and anti-counterfeiting of drugs. We firstly formulated three colored inks incorporating upconversion nanoparticles with RGB (i.e., red, green and blue) emission colors. Using a modified inkjet printer, we printed a series of colors by precisely regulating the overlap of these three inks. Meanwhile, we developed a multilayer printing and splitting technology, which significantly increases the information storage capacity per unit area. As an example, we directly printed the upconversion fluorescent 3D QR code on the surface of drug capsules. The 3D QR code consisted of three different color layers with each layer encoded by information of different aspects of the drug. A smart phone APP was designed to decode the multicolor 3D QR code, providing the authenticity and related information of drugs. The developed technology possesses merits in terms of low cost, ease of operation, high throughput and high information capacity, thus holds great potential for drug anti-counterfeiting.Medicine counterfeiting is a serious issue worldwide, involving potentially devastating health repercussions. Advanced anti-counterfeit technology for drugs has therefore aroused intensive interest. However, existing anti-counterfeit technologies are associated with drawbacks such as the high cost, complex fabrication process, sophisticated operation and incapability in authenticating drug ingredients. In this contribution, we developed a smart phone recognition based upconversion fluorescent three-dimensional (3D) quick response (QR) code for tracking and anti-counterfeiting of drugs. We firstly formulated three colored inks incorporating upconversion nanoparticles with RGB (i.e., red, green and blue) emission colors. Using a modified inkjet printer, we printed a series of colors by precisely regulating the overlap of these three inks. Meanwhile, we developed a multilayer printing and splitting technology, which significantly increases the information storage capacity per unit area. As an example, we directly printed the upconversion fluorescent 3D QR code on the surface of drug capsules. The 3D QR code consisted of three different color layers with each layer encoded by information of different aspects of the drug. A smart phone APP was designed to decode the multicolor 3D QR code, providing the authenticity and related information of drugs. The developed technology possesses merits in terms of low cost, ease of operation, high throughput and high information capacity, thus holds great potential for drug anti-counterfeiting. Electronic supplementary information (ESI) available: Calculating details of UCNP content per 3D QR code and decoding process of the 3D QR code. See DOI: 10.1039/c6nr01353h

Preparation and optical characteristics of ZnSe nanocrystals doped glass by sol gel in situ crystallization method

NASA Astrophysics Data System (ADS)

Hao, Haiyan; Yao, Xi; Wang, Minqiang

2007-01-01

Homogeneous ZnSe nanocrystals doped SiO 2 glass was successfully prepared by sol-gel in situ crystallization method. The structure of the doped ZnSe nanocrystals was studied by X-ray diffraction (XRD). ZnSe nanocrystals in silica were about 4-10 nm analysed by transmission electron microscopy (TEM), which was consistent with the results of XRD estimated using Scherrer's formular. The quantum size effect in ZnSe nanocrystals was evidenced from the blue-shifts of the optical absorption edge, and the average size of ZnSe nanocrystals was estimated by the magnitude of blue shift according to the L.E. Brus' effective mass model. The size of ZnSe nanocrystals depending on annealing time and temperature was further discussed using XRF.

Donor ionization in size controlled silicon nanocrystals: The transition from defect passivation to free electron generation

NASA Astrophysics Data System (ADS)

Crowe, I. F.; Papachristodoulou, N.; Halsall, M. P.; Hylton, N. P.; Hulko, O.; Knights, A. P.; Yang, P.; Gwilliam, R. M.; Shah, M.; Kenyon, A. J.

2013-01-01

We studied the photoluminescence spectra of silicon and phosphorus co-implanted silica thin films on (100) silicon substrates as a function of isothermal annealing time. The rapid phase segregation, formation, and growth dynamics of intrinsic silicon nanocrystals are observed, in the first 600 s of rapid thermal processing, using dark field mode X-TEM. For short annealing times, when the nanocrystal size distribution exhibits a relatively small mean diameter, formation in the presence of phosphorus yields an increase in the luminescence intensity and a blue shift in the emission peak compared with intrinsic nanocrystals. As the mean size increases with annealing time, this enhancement rapidly diminishes and the peak energy shifts further to the red than the intrinsic nanocrystals. These results indicate the existence of competing pathways for the donor electron, which depends strongly on the nanocrystal size. In samples containing a large density of relatively small nanocrystals, the tendency of phosphorus to accumulate at the nanocrystal-oxide interface means that ionization results in a passivation of dangling bond (Pb-centre) type defects, through a charge compensation mechanism. As the size distribution evolves with isothermal annealing, the density of large nanocrystals increases at the expense of smaller nanocrystals, through an Ostwald ripening mechanism, and the majority of phosphorus atoms occupy substitutional lattice sites within the nanocrystals. As a consequence of the smaller band-gap, ionization of phosphorus donors at these sites increases the free carrier concentration and opens up an efficient, non-radiative de-excitation route for photo-generated electrons via Auger recombination. This effect is exacerbated by an enhanced diffusion in phosphorus doped glasses, which accelerates silicon nanocrystal growth.

Energy Migration Upconversion in Manganese(II)-Doped Nanoparticles.

PubMed

Li, Xiyan; Liu, Xiaowang; Chevrier, Daniel M; Qin, Xian; Xie, Xiaoji; Song, Shuyan; Zhang, Hongjie; Zhang, Peng; Liu, Xiaogang

2015-11-02

We report the synthesis and characterization of cubic NaGdF4:Yb/Tm@NaGdF4:Mn core-shell structures. By taking advantage of energy transfer through Yb→Tm→Gd→Mn in these core-shell nanoparticles, we have realized upconversion emission of Mn(2+) at room temperature in lanthanide tetrafluoride based host lattices. The upconverted Mn(2+) emission, enabled by trapping the excitation energy through a Gd(3+) lattice, was validated by the observation of a decreased lifetime from 941 to 532 μs in the emission of Gd(3+) at 310 nm ((6)P(7/2)→(8)S(7/2)). This multiphoton upconversion process can be further enhanced under pulsed laser excitation at high power densities. Both experimental and theoretical studies provide evidence for Mn(2+) doping in the lanthanide-based host lattice arising from the formation of F(-) vacancies around Mn(2+) ions to maintain charge neutrality in the shell layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare-earth doped transparent nano-glass-ceramics: a new generation of photonic integrated devices

NASA Astrophysics Data System (ADS)

Rodríguez-Armas, Vicente Daniel; Tikhomirov, Victor K.; Méndez-Ramos, Jorge; Yanes, Angel C.; Del-Castillo, Javier; Furniss, David; Seddon, Angela B.

2007-05-01

We report on optical properties and prospect applications on rare-earth doped oxyfluoride precursor glass and ensuing nano-glass-ceramics. We find out the spectral optical gain of the nano-glass-ceramics and show that its flatness and breadth are advantageous as compared to contemporary used erbium doped optical amplifiers. We present the possibility of flat gain cross-section erbium doped waveguide amplifiers as short 'chip', all-optical, devices capable of dense wavelength division multiplexing, including the potential for direct writing of these devices inside bulk glasses for three-dimensional photonic integration. We carried out a comparative study of the up-conversion luminescence in Er 3+-doped and Yb 3+-Er 3+-Tm 3+ co-doped samples, which indicates that these materials can be used as green/red tuneable up-conversion phosphors and white light simulation respectively. Observed changes in the spectra of the up-conversion luminescence provide a tool for tuning the colour opening the way for producing 3-dimensional optical recording.

Clean synthesis of YOF:Er3+, Yb3+ upconversion colloidal nanoparticles in water through liquid phase pulsed laser ablation for imaging applications

NASA Astrophysics Data System (ADS)

Anjana, R.; Kurias, K. M.; Jayaraj, M. K.

2017-10-01

Upconversion luminescent nanomaterials have great outlook towards imaging applications. These materials have high chemical and thermal stability, low auto fluorescence, high photo stability and IR excitation does not cause photo damage to living cells and penetrate deeply into tissue. Most of the reported nanoparticles are synthesized through chemical methods in which surface modification is needed for dispersing nanoparticles in water. In this paper we report clean and simple synthesis of upconversion luminescent yttrium oxyfluoride (YOF) nanoparticles through laser ablation in deionized water. YOF:Er3+, Yb3+ pellets were used for ablation. Er3+ is the emission centre Yb3+ is the sensitizer. Obtained colloidal solution is transparent to day light and showing red emission on exciting with 980 nm IR laser. By controlling ablation parameters particles of size less than 10 nm dispersed uniformly in water can be obtained through this surfactant free method. The synthesized nanoparticles can be used for cell imaging.

Photoemission of Energetic Hot Electrons Produced via Up-Conversion in Doped Quantum Dots.

PubMed

Dong, Yitong; Parobek, David; Rossi, Daniel; Son, Dong Hee

2016-11-09

The benefits of the hot electrons from semiconductor nanostructures in photocatalysis or photovoltaics result from their higher energy compared to that of the band-edge electrons facilitating the electron-transfer process. The production of high-energy hot electrons usually requires short-wavelength UV or intense multiphoton visible excitation. Here, we show that highly energetic hot electrons capable of above-threshold ionization are produced via exciton-to-hot-carrier up-conversion in Mn-doped quantum dots under weak band gap excitation (∼10 W/cm 2 ) achievable with the concentrated solar radiation. The energy of hot electrons is as high as ∼0.4 eV above the vacuum level, much greater than those observed in other semiconductor or plasmonic metal nanostructures, which are capable of performing energetically and kinetically more-challenging electron transfer. Furthermore, the prospect of generating solvated electron is unique for the energetic hot electrons from up-conversion, which can open a new door for long-range electron transfer beyond short-range interfacial electron transfer.

Photon correlation in single-photon frequency upconversion.

PubMed

Gu, Xiaorong; Huang, Kun; Pan, Haifeng; Wu, E; Zeng, Heping

2012-01-30

We experimentally investigated the intensity cross-correlation between the upconverted photons and the unconverted photons in the single-photon frequency upconversion process with multi-longitudinal mode pump and signal sources. In theoretical analysis, with this multi-longitudinal mode of both signal and pump sources system, the properties of the signal photons could also be maintained as in the single-mode frequency upconversion system. Experimentally, based on the conversion efficiency of 80.5%, the joint probability of simultaneously detecting at upconverted and unconverted photons showed an anti-correlation as a function of conversion efficiency which indicated the upconverted photons were one-to-one from the signal photons. While due to the coherent state of the signal photons, the intensity cross-correlation function g(2)(0) was shown to be equal to unity at any conversion efficiency, agreeing with the theoretical prediction. This study will benefit the high-speed wavelength-tunable quantum state translation or photonic quantum interface together with the mature frequency tuning or longitudinal mode selection techniques.

Enabling valley selective exciton scattering in monolayer WSe2 through upconversion

PubMed Central

Manca, M.; Glazov, M. M.; Robert, C.; Cadiz, F.; Taniguchi, T.; Watanabe, K.; Courtade, E.; Amand, T.; Renucci, P.; Marie, X.; Wang, G.; Urbaszek, B.

2017-01-01

Excitons, Coulomb bound electron–hole pairs, are composite bosons and their interactions in traditional semiconductors lead to condensation and light amplification. The much stronger Coulomb interaction in transition metal dichalcogenides such as WSe2 monolayers combined with the presence of the valley degree of freedom is expected to provide new opportunities for controlling excitonic effects. But so far the bosonic character of exciton scattering processes remains largely unexplored in these two-dimensional materials. Here we show that scattering between B-excitons and A-excitons preferably happens within the same valley in momentum space. This leads to power dependent, negative polarization of the hot B-exciton emission. We use a selective upconversion technique for efficient generation of B-excitons in the presence of resonantly excited A-excitons at lower energy; we also observe the excited A-excitons state 2s. Detuning of the continuous wave, low-power laser excitation outside the A-exciton resonance (with a full width at half maximum of 4 meV) results in vanishing upconversion signal. PMID:28367962

Long wavelength identification of microcalcifications in breast cancer tissue using a quantum cascade laser and upconversion detection

NASA Astrophysics Data System (ADS)

Tseng, Y. P.; Bouzy, P.; Stone, N.; Pedersen, C.; Tidemand-Lichtenberg, P.

2018-02-01

Spectral imaging in the long-wave infrared regime has great potential for medical diagnostics. Breast cancer is the most common cancer amongst females in the US. The pathological features and the occurrence of the microcalcifications are still poorly understood. However, two types of microcalcifications have been identified as unique biomarkers: type I consisting of calcium oxalate (benign lesions) and type II composed of hydroxyapatite (benign or invasive lesions). In this study, we propose a new approach based on vibrational spectroscopy that is non-destructive, label-free and chemically specific for breast cancer detection. Long-wave infrared spectroscopy combining quantum cascade lasers (QCL) and upconversion detection, offer to improve signal-to-noise ratios compared to standard long-wave infrared spectroscopy. We demonstrated long-wave identification of synthetic samples of carbonated hydroxyapatite and of microcalcification in breast cancer tissue using upconversion detection. Absorbance spectra and upconverted images of in situ breast cancer biopsy are compared with that of Fourier-transform infrared (FTIR) spectroscopy.

(Bio)hybrid materials based on optically active particles

NASA Astrophysics Data System (ADS)

Reitzig, Manuela; Härtling, Thomas; Opitz, Jörg

2014-03-01

In this contribution we provide an overview of current investigations on optically active particles (nanodiamonds, upconversion phospors) for biohybrid and sensing applications. Due to their outstanding properties nanodiamonds gain attention in various application elds such as microelectronics, optical monitoring, medicine, and biotechnology. Beyond the typical diamond properties such as high thermal conductivity and extreme hardness, the carbon surface and its various functional groups enable diverse chemical and biological surface functionalization. At Fraunhofer IKTS-MD we develop a customization of material surfaces via integration of chemically modi ed nanodiamonds at variable surfaces, e.g bone implants and pipelines. For the rst purpose, nanodiamonds are covalently modi ed at their surface with amino or phosphate functionalities that are known to increase adhesion to bone or titanium alloys. The second type of surface is approached via mechanical implementation into coatings. Besides nanodiamonds, we also investigate the properties of upconversion phosphors. In our contribution we show how upconversion phosphors are used to verify sterilization processes via a change of optical properties due to sterilizing electron beam exposure.

The Surface Chemistry of Metal Chalcogenide Nanocrystals

NASA Astrophysics Data System (ADS)

Anderson, Nicholas Charles

The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu3P complex of cadmium chloride. Nuclear magnetic resonance spectroscopy supports complete cleavage of the X-type carboxylate ligands. Combined with measurements of the Se:Cd:Cl ratio using Rutherford backscattering spectrometry, these studies support a structural model of nanocrystals where chloride ligands terminate the crystal lattice by balancing the charges of excess Cd2+ ions. The adsorption of dative phosphine ligands leads to nanocrystals who's solubility is afforded by reversibly bound and readily exchanged L-type ligands, e.g. primary amines and phosphines. The other halides (Br and I) can also be used to prepare Bu 3P-bound, halide-terminated CdSe nanocrystals, however these nanocrystals are not soluble after exchange. The change in binding affinity of Bu 3P over the halide series is briefly discussed. Next, we report a series of L-type ligand exchanges using Bu3P-bound, chloride-terminated CdSe nanocrystals with several Lewis bases, including aromatic, cyclic, and non-cyclic sulfides, and ethers; primary, secondary, and tertiary amines and phosphines; tertiary phosphine chalcogenides; primary alcohols, isocyanides, and isothiocyanides. Using 31P nuclear magnetic resonance spectroscopy, we establish a relative binding affinity for these ligands that reflects electronic considerations but is dominated primarily by steric interactions, as determined by comparing binding affinity to Tolmann cone angles. We also used chloride-terminated CdSe nanocrystals to explore the reactivity of ionic salts at nanocrystal surfaces. These salts, particularly [Bu3P-H]+[Cl]-, bind nanocrystals surfaces as L-type ligands, making them soluble in polar solvents such as acetonitrile. This information should provide insight for rational ligand design for future applications involving metal chalcogenide nanocrystals. The strongest ligand, primary n-alkylamine, rapidly displace the Bu3P from halide-terminated CdSe nanocrystals, leading to amine-bound nanocrystals with higher dative ligand coverages and greatly increased photoluminescence quantum yields. The importance of ligand coverage to both the UV-visible absorption and photoluminescence spectra are discussed. (Abstract shortened by UMI.).

2-Hydroxypropyltrimethylammonium xylan adsorption onto rod-like cellulose nanocrystal.

PubMed

Sim, Jae Hyun; Dong, Shuping; Röemhild, Katrin; Kaya, Abdulaziz; Sohn, Daewon; Tanaka, Keiji; Roman, Maren; Heinze, Thomas; Esker, Alan R

2015-02-15

Chemical incompatibility and relatively weak interaction between lignocellulosic fibers and synthetic polymers have made studies of wood fiber-thermoplastic composite more challenging. In this study, adsorption of 2-hydroxypropyltrimethylammonium xylans onto rod-like cellulose nanocrystals are investigated by zeta-potential measurements, and polarized and depolarized dynamic light scattering as a factor for better understanding of lignocellulosic fibers and cellulose nanocrystals. Zeta-potential measurements show xylan derivative adsorption onto cellulose nanocrystals. Decay time distributions of the ternary system and binary system from dynamic light scattering show that aggregates exist in the binary system and they disappear in the ternary system. At low 2-hydroxypropyltrimethylammonium xylan concentrations relative to that of cellulose nanocrystal, xylan derivatives adsorbed onto some of the cellulose nanocrystal. Hence, more xylan derivatives adsorbed onto cellulose nanocrystal increased with increasing xylan derivative concentration. Also, the concentration dependence of the ratio of the rotational diffusion coefficient to the translational diffusion coefficient revealed a strong adsorptive interaction between xylan derivatives and the cellulose nanocrystals. Copyright © 2014 Elsevier Inc. All rights reserved.

Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals.

PubMed

Bardhan, Rizia; Hedges, Lester O; Pint, Cary L; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J

2013-10-01

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

Correlation between CdSe QD Synthesis, Post-Synthetic Treatment, and BHJ Hybrid Solar Cell Performance

PubMed Central

Eck, Michael; Krueger, Michael

2016-01-01

In this publication we show that the procedure to synthesize nanocrystals and the post-synthetic nanocrystal ligand sphere treatment have a great influence not only on the immediate performance of hybrid bulk heterojunction solar cells, but also on their thermal, long-term, and air stability. We herein demonstrate this for the particular case of spherical CdSe nanocrystals, post-synthetically treated with a hexanoic acid based treatment. We observe an influence from the duration of this post-synthetic treatment on the nanocrystal ligand sphere size, and also on the solar cell performance. By tuning the post-synthetic treatment to a certain degree, optimal device performance can be achieved. Moreover, we show how to effectively adapt the post-synthetic nanocrystal treatment protocol to different nanocrystal synthesis batches, hence increasing the reproducibility of hybrid nanocrystal:polymer bulk-heterojunction solar cells, which usually suffers due to the fluctuations in nanocrystal quality of different synthesis batches and synthesis procedures. PMID:28335243

Quantum confinement of nanocrystals within amorphous matrices

NASA Astrophysics Data System (ADS)

Lusk, Mark T.; Collins, Reuben T.; Nourbakhsh, Zahra; Akbarzadeh, Hadi

2014-02-01

Nanocrystals encapsulated within an amorphous matrix are computationally analyzed to quantify the degree to which the matrix modifies the nature of their quantum-confinement power—i.e., the relationship between nanocrystal size and the gap between valence- and conduction-band edges. A special geometry allows exactly the same amorphous matrix to be applied to nanocrystals of increasing size to precisely quantify changes in confinement without the noise typically associated with encapsulating structures that are different for each nanocrystal. The results both explain and quantify the degree to which amorphous matrices redshift the character of quantum confinement. The character of this confinement depends on both the type of encapsulating material and the separation distance between the nanocrystals within it. Surprisingly, the analysis also identifies a critical nanocrystal threshold below which quantum confinement is not possible—a feature unique to amorphous encapsulation. Although applied to silicon nanocrystals within an amorphous silicon matrix, the methodology can be used to accurately analyze the confinement softening of other amorphous systems as well.

Necessary conditions for superior thermoelectric power of Si/Au artificial superlattice thin-film

NASA Astrophysics Data System (ADS)

Okamoto, Yoichi; Watanabe, Shin; Miyazaki, Hisashi; Morimoto, Jun

2018-03-01

The Si-Ge-Au ternary artificial superlattice thin-films showed superior thermoelectric power with low reproducibility. Superior thermoelectric power was only generated, when nanocrystals existed. Therefore, the origin of superior thermoelectric power was considered to be the quantum size effect of nanocrystals. However, even with the presence of nanocrystals, superior thermoelectric power was often not generated. In order to investigate the generation conditions of superior thermoelectric power in more detail, the samples were simplified to Si-Au binary artificial superlattice samples. Furthermore, annealings were carried out under conditions where nanocrystals were likely to be formed. From the results of Raman scattering spectroscopy and X-ray diffraction (XRD) analysis, the diameter of nanocrystals and the spacing between nanocrystals were calculated with an isotropic three-dimensional mosaic model. It was found that superior thermoelectric power was generated only when the diameter of nanocrystals was 11 nm or less and the spacing between nanocrystals was 3 nm or less.

Optical determination of crystal phase in semiconductor nanocrystals

PubMed Central

Lim, Sung Jun; Schleife, André; Smith, Andrew M.

2017-01-01

Optical, electronic and structural properties of nanocrystals fundamentally derive from crystal phase. This is especially important for polymorphic II–VI, III–V and I-III-VI2 semiconductor materials such as cadmium selenide, which exist as two stable phases, cubic and hexagonal, each with distinct properties. However, standard crystallographic characterization through diffraction yields ambiguous phase signatures when nanocrystals are small or polytypic. Moreover, diffraction methods are low-throughput, incompatible with solution samples and require large sample quantities. Here we report the identification of unambiguous optical signatures of cubic and hexagonal phases in II–VI nanocrystals using absorption spectroscopy and first-principles electronic-structure theory. High-energy spectral features allow rapid identification of phase, even in small nanocrystals (∼2 nm), and may help predict polytypic nanocrystals from differential phase contributions. These theoretical and experimental insights provide simple and accurate optical crystallographic analysis for liquid-dispersed nanomaterials, to improve the precision of nanocrystal engineering and improve our understanding of nanocrystal reactions. PMID:28513577

Nanocrystal/sol-gel nanocomposites

DOEpatents

Klimov, Victor L.; Petruska, Melissa A.

2010-05-25

The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

Increased electronic coupling in silicon nanocrystal networks doped with F4-TCNQ.

PubMed

Carvalho, Alexandra; Oberg, Sven; Rayson, Mark J; Briddon, Patrick R

2013-02-01

The modification of the electronic structure of silicon nanocrystals using an organic dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), is investigated using first-principles calculations. It is shown that physisorbed F4-TCNQ molecules have the effect of oxidizing the nanocrystal, attracting the charge density towards the F4-TCNQ-nanocrystal interface, and decreasing the excitation energy of the system. In periodic F4-TCNQ/nanocrystal superlattices, F4-TCNQ is suggested to enhance exciton separation, and in the presence of free holes, to serve as a bridge for electron/hole transfer between adjacent nanocrystals.

A New Method for Delivering a Hydrophobic Drug for Photodynamic Therapy Using Pure Nanocrystal Form of the Drug

PubMed Central

Baba, Koichi; Pudavar, Haridas E.; Roy, Indrajit; Ohulchanskyy, Tymish Y.; Chen, Yihui; Pandey, Ravindra; Prasad, Paras N.

2008-01-01

A carrier free method for delivery of a hydrophobic drug in its pure form, using nanocrystals (nano sized crystals) is proposed. To demonstrate this technique, nanocrystals of a hydrophobic photosensitizing anticancer drug 2-devinyl-2-(1-hexyloxyethyl)pyropheophorbide (HPPH), have been synthesized using re-precipitation method. The resulting drug nanocrystals were monodispersed and stable in aqueous dispersion, without the necessity of an additional stabilizer (surfactant). As shown by confocal microscopy, these pure drug nanocrystals were taken-up by the cancer cells with high avidity. Though the fluorescence and photodynamic activity of the drug were substantially quenched in the form of nanocrystals in aqueous suspension, both these characteristics were recovered under in vitro and in vivo conditions. This recovery of drug activity and fluorescence is possibly due to the interaction of nanocrystals with serum albumin, resulting in conversion of the drug nanocrystals into the molecular form. This was confirmed by demonstrating similar recovery in presence of Fetal Bovine Serum (FBS) or Bovine Serum Albumin (BSA). Under similar treatment conditions, the HPPH in nanocrystal form or in 1% Tween 80/water formulation showed comparable in vitro and in vivo efficacy. PMID:17266331

A pH-Sensitive, Biobased Calcium Carbonate Aragonite Nanocrystal as a Novel Anticancer Delivery System

PubMed Central

Ismail, Maznah; Tengku Ibrahim, Tengku Azmi; Zakaria, Zuki Abu Bakar

2013-01-01

The synthesised biobased calcium carbonate nanocrystals had demonstrated to be an effective carrier for delivery of anticancer drug doxorubicin (DOX). The use of these nanocrystals displayed high levels of selectivity and specificity in achieving effective cancer cell death without nonspecific toxicity. These results confirmed that DOX was intercalated into calcium carbonate nanocrystals at high loading and encapsulation efficiency (4.8 and 96%, resp.). The CaCO3/DOX nanocrystals are relatively stable at neutral pH (7.4), resulting in slow release, but the nanocrystals progressively dissociated in acidic pH (4.8) regimes, triggering faster release of DOX. The CaCO3/DOX nanocrystals exhibited high uptake by MDA MB231 breast cancer cells and a promising potential delivery of DOX to target cells. In vitro chemosensitivity using MTT, modified neutral red/trypan blue assay, and LDH on MDA MB231 breast cancer cells revealed that CaCO3/DOX nanocrystals are more sensitive and gave a greater reduction in cell growth than free DOX. Our findings suggest that CaCO3 nanocrystals hold tremendous promise in the areas of controlled drug delivery and targeted cancer therapy. PMID:24324966

A Radiation-Tolerant, Low-Power Non-Volatile Memory Based on Silicon Nanocrystal Quantum Dots

NASA Technical Reports Server (NTRS)

Bell, L. D.; Boer, E. A.; Ostraat, M. L.; Brongersma, M. L.; Flagan, R. C.; Atwater, H. A.; deBlauwe, J.; Green, M. L.

2001-01-01

Nanocrystal nonvolatile floating-gate memories are a good candidate for space applications - initial results suggest they are fast, more reliable and consume less power than conventional floating gate memories. In the nanocrystal based NVM device, charge is not stored on a continuous polysilicon layer (so-called floating gate), but instead on a layer of discrete nanocrystals. Charge injection and storage in dense arrays of silicon nanocrystals in SiO2 is a critical aspect of the performance of potential nanocrystal flash memory structures. The ultimate goal for this class of devices is few- or single-electron storage in a small number of nanocrystal elements. In addition, the nanocrystal layer fabrication technique should be simple, 8-inch wafer compatible and well controlled in program/erase threshold voltage swing was seen during 100,000 program and erase cycles. Additional near-term goals for this project include extensive testing for radiation hardness and the development of artificial layered tunnel barrier heterostructures which have the potential for large speed enhancements for read/write of nanocrystal memory elements, compared with conventional flash devices. Additional information is contained in the original extended abstract.

Nanomagnetism study of highly-ordered iron oxide nanocrystal assemblies fabricated by the Langmuir-Blodgett technique.

PubMed

Zhang, HaiTao; Bao, NiNa; Yuan, Du; Ding, Jun

2013-09-21

Iron oxide nanocrystals are ideal building blocks for the construction of flexible nanodevices whose performance can be modulated by controlling the morphology of isolated particles and their organizational form. This work demonstrates the fabrication of high quality Langmuir-Blodgett (LB) nanocrystal assemblies with limited overlapping and higher coverage by systemically and combinatorially optimizing the parameters of compression pressure and quantity of spread nanocrystals. Monodispersed iron oxide nanocrystals with a diameter of 11.8 nm were synthesized by thermal decomposition of Fe(CO)5 in trioctylamine with the presence of oleic acid. Multilayer nanocrystal assemblies were obtained through a layer-by-layer (LBL) process by repeating the transfer procedure after their hydrophilicity had been improved via treatment in a UV-ozone oven. The quality of nanocrystal assemblies was investigated by UV-vis spectrometry and scanning electron microscopy. The nanomagnetism for the nanostructures of different combination manners was studied systemically by a superconducting quantum interference device (SQUID). A lower superparamagnetic blocking temperature was found in the monolayer Fe3O4 nanocrystal assembly. The superparamagnetic blocking temperature in magnetic nanocrystal assemblies could be tuned through modifying the interparticle interactions among the interlayer and intralayers by controlling the layer number of the assemblies.

Delivery and reveal of localization of upconversion luminescent microparticles and quantum dots in the skin in vivo by fractional laser microablation, multimodal imaging, and optical clearing.

PubMed

Volkova, Elena K; Yanina, Irina Yu; Genina, Elina A; Bashkatov, Alexey N; Konyukhova, Julia G; Popov, Alexey P; Speranskaya, Elena S; Bucharskaya, Alla B; Navolokin, Nikita A; Goryacheva, Irina Yu; Kochubey, Vyacheslav I; Sukhorukov, Gleb B; Meglinski, Igor V; Tuchin, Valery V

2018-02-01

Delivery and spatial localization of upconversion luminescent microparticles [Y2O3:Yb, Er] (mean size ∼1.6  μm) and quantum dots (QDs) (CuInS2/ZnS nanoparticles coated with polyethylene glycol-based amphiphilic polymer, mean size ∼20  nm) inside rat skin was studied in vivo using a multimodal optical imaging approach. The particles were embedded into the skin dermis to the depth from 300 to 500  μm through microchannels performed by fractional laser microablation. Low-frequency ultrasound was applied to enhance penetration of the particles into the skin. Visualization of the particles was revealed using a combination of luminescent spectroscopy, optical coherence tomography, confocal microscopy, and histochemical analysis. Optical clearing was used to enhance the image contrast of the luminescent signal from the particles. It was demonstrated that the penetration depth of particles depends on their size, resulting in a different detection time interval (days) of the luminescent signal from microparticles and QDs inside the rat skin in vivo. We show that luminescent signal from the upconversion microparticles and QDs was detected after the particle delivery into the rat skin in vivo during eighth and fourth days, respectively. We hypothesize that the upconversion microparticles have created a long-time depot localized in the laser-created channels, as the QDs spread over the surrounding tissues. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Explanation of the cw operation of the Er3+ 3-μm crystal laser

NASA Astrophysics Data System (ADS)

Pollnau, M.; Graf, Th.; Balmer, J. E.; Lüthy, W.; Weber, H. P.

1994-05-01

A computer simulation of the Er3+ 3-μm crystal laser considering the full rate-equation scheme up to the 4F7/2 level has been performed. The influence of the important system parameters on lasing and the interaction of these parameters has been clarified with multiple-parameter variations. Stimulated emission is fed mainly by up-conversion from the lower laser level and in many cases is reduced by the quenching of the lifetime of this level. However, also without up-conversion a set of parameters can be found that allows lasing. Up-conversion from the upper laser level is detrimental to stimulated emission but may be compensated by cross relaxation from the 4S3/2 level. For a typical experimental situation we started with the parameters of Er3+:LiYF4. In addition, the host materials Y3Al5O12 (YAG), YAlO3, Y3Sc2Al3O12 (YSGG), and BaY2F8, as well as the possibilities of codoping, are discussed. In view of the consideration of all excited levels up to 4F7/2, all lifetimes and branching ratios, ground-state depletion, excited-state absorption, three up-conversion processes as well as their inverse processes, stimulated emission, and a realistic resonator design, this is, to our knowledge, the most detailed investigation of the Er3+ 3-μm crystal laser performed so far.

Bioinspired near-infrared-excited sensing platform for in vitro antioxidant capacity assay based on upconversion nanoparticles and a dopamine-melanin hybrid system.

PubMed

Wang, Dong; Chen, Chuan; Ke, Xuebin; Kang, Ning; Shen, Yuqing; Liu, Yongliang; Zhou, Xi; Wang, Hongjun; Chen, Changqing; Ren, Lei

2015-02-11

A novel core-shell structure based on upconversion fluorescent nanoparticles (UCNPs) and dopamine-melanin has been developed for evaluation of the antioxidant capacity of biological fluids. In this approach, dopamine-melanin nanoshells facilely formed on the surface of UCNPs act as ultraefficient quenchers for upconversion fluorescence, contributing to a photoinduced electron-transfer mechanism. This spontaneous oxidative polymerization of the dopamine-induced quenching effect could be effectively prevented by the presence of various antioxidants (typically biothiols, ascorbic acid (Vitamin C), and Trolox). The chemical response of the UCNPs@dopamine-melanin hybrid system exhibited great selectivity and sensitivity toward antioxidants relative to other compounds at 100-fold higher concentration. A satisfactory correlation was established between the ratio of the "anti-quenching" fluorescence intensity and the concentration of antioxidants. Besides the response of the upconversion fluorescence signal, a specific evaluation process for antioxidants could be visualized by the color change from colorless to dark gray accompanied by the spontaneous oxidation of dopamine. The near-infrared (NIR)-excited UCNP-based antioxidant capacity assay platform was further used to evaluate the antioxidant capacity of cell extracts and human plasma, and satisfactory sensitivity, repeatability, and recovery rate were obtained. This approach features easy preparation, fluorescence/visual dual mode detection, high specificity to antioxidants, and enhanced sensitivity with NIR excitation, showing great potential for screening and quantitative evaluation of antioxidants in biological systems.

Triplet-Triplet Annihilation Photon Upconversion in Polymer Thin Film: Sensitizer Design.

PubMed

Jiang, Xinpeng; Guo, Xinyan; Peng, Jiang; Zhao, Dahui; Ma, Yuguo

2016-05-11

Efficient visible-to-UV photon upconversion via triplet-triplet annihilation (TTA) is accomplished in polyurethane (PU) films by developing new, powerful photosensitizers fully functional in the solid-state matrix. These rationally designed triplet sensitizers feature a bichromophoric scaffold comprising a tris-cyclometalated iridium(III) complex covalently tethered to a suitable organic small molecule. The very rapid intramolecular triplet energy transfer from the former to the latter is pivotal for achieving the potent sensitizing ability, because this process out-competes the radiative and nonradiative decays inherent to the metal complex and produces long-lived triplet excitons localized with the acceptor moiety readily available for intermolecular transfer and TTA. Nonetheless, compared to the solution state, the molecular diffusion is greatly limited in solid matrices, which even creates difficulty for the Dexter-type intramolecular energy transfer. This is proven by the experimental results showing that the sensitizing performance of the bichromophoric molecules strongly depends on the spatial distance separating the donor (D) and acceptor (A) units and that incorporating a longer linker between the D and A evidently curbs the TTA upconversion efficiency in PU films. Using a rationally optimized sensitizer structure in combination with 2,7-di-tert-butylpyrene as the annihilator/emitter, the doped polyurethane (PU) films demonstrate effective visible-to-UV upconverted emission signal under noncoherent-light irradiation, attaining an upconversion quantum yield of 2.6%. Such quantum efficiency is the highest value so far reported for the visible-to-UV TTA systems in solid matrices.

Charge transport in metal oxide nanocrystal-based materials

NASA Astrophysics Data System (ADS)

Runnerstrom, Evan Lars

There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and structure. Charge transport can obviously be taken to mean the conduction of electrons, but it also refers to the motion of ions, such as lithium ions and protons. In many cases, the transport of ions is married to the motion of electrons as well, either through an external electrical circuit, or within the same material in the case of mixed ionic electronic conductors. The collective motion of electrons over short length scales, that is, within single nanocrystals, is also a subject of study as it pertains to plasmonic nanocrystals. Finally, charge transport can also be coupled to or result from the formation of defects in metal oxides. All of these modes of charge transport in metal oxides gain further complexity when considered in nanocrystalline systems, where the introduction of numerous surfaces can change the character of charge transport relative to bulk systems, providing opportunities to exploit new physical phenomena. Part I of this dissertation explores the combination of electronic and ionic transport in electrochromic devices based on nanocrystals. Colloidal chemistry and solution processing are used to fabricate nanocomposites based on electrochromic tin-doped indium oxide (ITO) nanocrystals. The nanocomposites, which are completely synthesized using solution processing, consist of ITO nanocrystals and lithium bis(trifluoromethylsulfonyl)amide (LiTFSI) salt dispersed in a lithium ion-conducting polymer matrix of either poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA). ITO nanocrystals are prepared by colloidal synthetic methods and the nanocrystal surface chemistry is modified to achieve favorable nanocrystal-polymer interactions. Homogeneous solutions containing polymer, ITO nanocrystals, and lithium salt are thus prepared and deposited by spin casting. Characterization by DC electronic measurements, microscopy, and x-ray scattering techniques show that the ITO nanocrystals form a complete, connected electrode within a polymer electrolyte matrix, and that the morphology and properties of the nanocomposites can be manipulated by changing the chemical composition of the deposition solution. Careful application of AC impedance spectroscopy techniques and DC measurements are used to show that the nanocomposites exhibit mixed ionic and electronic conductivity, where electronic charge is transported through the ITO nanocrystal phase, and ionic charge is transported through the polymer matrix phase. The synthetic methods developed here and understanding of charge transport ultimately lead to the fabrication of a solid state nanocomposite electrochromic device based on nanocrystals of ITO and cerium oxide. Part II of this dissertation considers electron transport within individual metal oxide nanocrystals themselves. It primarily examines relationships between synthetic chemistry, doping mechanisms in metal oxides, and the accompanying physics of free carrier scattering within the interior of highly doped metal oxide nanocrystals, with particular mind paid to ITO nanocrystals. Additionally, synthetic methods as well as metal oxide defect chemistry influences the balance between activation and compensation of dopants, which limits the nanocrystals' free carrier concentration. Furthermore, because of ionized impurity scattering of the oscillating electrons by dopant ions, scattering must be treated in a fundamentally different way in semiconductor metal oxide materials when compared with conventional metals. (Abstract shortened by ProQuest.).

A facile arrested precipitation method for synthesis of pure wurtzite Cu{sub 2}ZnSnS{sub 4} nanocrystals using thiourea as a sulfur source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Chunya; Key Laboratory of Analytical Chemistry of the State Ethnic Affairs Commission, College of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan 430074; Ha, Enna

2012-11-15

Graphical abstract: High-resolution TEM image of wurtzite Cu{sub 2}ZnSnS{sub 4} nanocrystals. Highlights: ► Wurtzite Cu{sub 2}ZnSnS{sub 4} nanocrystals were synthesized by arrested precipitation method. ► XRD, EDX, TEM demonstrate that the CZTS nanocrystals are purely wurtzite structure. ► The average diameter of the bulk CZTS products is found to be 10 ± 1.1 nm. ► The estimated direct bandgap energy is 1.56 eV for wurtzite CZTS nanocrystals. ► The electrical resistivity of the wurtzite CZTS nanocrystals is low. -- Abstract: A facile route for the synthesis of wurtzite Cu{sub 2}ZnSnS{sub 4} (CZTS) nanocrystals was developed by an arrested precipitation methodmore » at 240 °C under simple reaction conditions with diethanolamine as the solvent and thiourea as sulfur source. The structure and morphology of the CZTS nanocrystals were characterized by X-ray diffraction and transmission electron microscopy. Control experiments demonstrated that CZTS nanocrystals which are purely wurtzite structure are readily obtained. The average diameter of the bulk CZTS products is found to be 10 ± 1.1 nm. The estimated direct bandgap energy is 1.56 eV, which indicates that the CZTS nanocrystals produced by this method possess promising applications in photovoltaic devices.« less

Novel silica stabilization method for the analysis of fine nanocrystals using coherent X-ray diffraction imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monteforte, Marianne; Estandarte, Ana K.; Chen, Bo

2016-06-23

High-energy X-ray Bragg coherent diffraction imaging (BCDI) is a well established synchrotron-based technique used to quantitatively reconstruct the three-dimensional morphology and strain distribution in nanocrystals. The BCDI technique has become a powerful analytical tool for quantitative investigations of nanocrystals, nanotubes, nanorods and more recently biological systems. BCDI has however typically failed for fine nanocrystals in sub-100?nm size regimes ? a size routinely achievable by chemical synthesis ? despite the spatial resolution of the BCDI technique being 20?30?nm. The limitations of this technique arise from the movement of nanocrystals under illumination by the highly coherent beam, which prevents full diffraction datamore » sets from being acquired. A solution is provided here to overcome this problem and extend the size limit of the BCDI technique, through the design of a novel stabilization method by embedding the fine nanocrystals into a silica matrix. Chemically synthesized FePt nanocrystals of maximum dimension 20?nm and AuPd nanocrystals in the size range 60?65?nm were investigated with BCDI measurement at beamline 34-ID-C of the APS, Argonne National Laboratory. Novel experimental methodologies to elucidate the presence of strain in fine nanocrystals are a necessary pre-requisite in order to better understand strain profiles in engineered nanocrystals for novel device development.« less

Novel silica stabilization method for the analysis of fine nanocrystals using coherent X-ray diffraction imaging.

PubMed

Monteforte, Marianne; Estandarte, Ana K; Chen, Bo; Harder, Ross; Huang, Michael H; Robinson, Ian K

2016-07-01

High-energy X-ray Bragg coherent diffraction imaging (BCDI) is a well established synchrotron-based technique used to quantitatively reconstruct the three-dimensional morphology and strain distribution in nanocrystals. The BCDI technique has become a powerful analytical tool for quantitative investigations of nanocrystals, nanotubes, nanorods and more recently biological systems. BCDI has however typically failed for fine nanocrystals in sub-100 nm size regimes - a size routinely achievable by chemical synthesis - despite the spatial resolution of the BCDI technique being 20-30 nm. The limitations of this technique arise from the movement of nanocrystals under illumination by the highly coherent beam, which prevents full diffraction data sets from being acquired. A solution is provided here to overcome this problem and extend the size limit of the BCDI technique, through the design of a novel stabilization method by embedding the fine nanocrystals into a silica matrix. Chemically synthesized FePt nanocrystals of maximum dimension 20 nm and AuPd nanocrystals in the size range 60-65 nm were investigated with BCDI measurement at beamline 34-ID-C of the APS, Argonne National Laboratory. Novel experimental methodologies to elucidate the presence of strain in fine nanocrystals are a necessary pre-requisite in order to better understand strain profiles in engineered nanocrystals for novel device development.

Improved oral bioavailability for lutein by nanocrystal technology: formulation development, in vitro and in vivo evaluation.

PubMed

Chang, Daoxiao; Ma, Yanni; Cao, Guoyu; Wang, Jianhuan; Zhang, Xia; Feng, Jun; Wang, Wenping

2018-08-01

Lutein is a kind of natural carotenoids possessing many pharmacological effects. The application of lutein was limited mainly due to its low oral bioavailability caused by poor aqueous solubility. Nanocrystal formulation of lutein was developed to improve the oral bioavailability in this study. The nanosuspension was prepared by the anti-solvent precipitation-ultrasonication method and optimized by Box-Behnken design, followed by freeze-drying to obtain lutein nanocrystals. The nanocrystals were characterized on their physical properties, in vitro dissolution and in vivo absorption performance. Lutein nanocrystals showed as tiny spheres with an average particle size of 110.7 nm. The result of diffractograms indicated that the percent crystallinity of lutein was 89.4% in coarse powder and then declined in nanocrystal formulation. The saturated solubility of lutein in water increased from 7.3 μg/ml for coarse powder up to 215.7 μg/ml for lutein nanocrystals. The dissolution rate of lutein nanocrystals was significantly higher than that of coarse powder or the physical mixture. The C max and AUC 0-24 h of lutein nanocrystals after oral administration in rats was 3.24 and 2.28 times higher than those of lutein suspension, respectively. These results indicated that the nanocrystal formulation could significantly enhance the dissolution and absorption of lutein and might be a promising approach for improving its oral bioavailability.

Nanocrystallization in Fluorochlorozirconate Glass-Ceramics.

PubMed

Alvarez, Carlos J; Liu, Yuzi; Leonard, Russell L; Johnson, Jacqueline A; Petford-Long, Amanda K

2013-11-01

Heat treating fluorochlorozirconate (FCZ) glasses nucleates nanocrystals in the glass matrix, resulting in a nanocomposite glass-ceramic that has optical properties suitable for use as a medical imaging plate. Understanding the way in which the nanocrystal nucleation proceeds is critical to controlling the optical behavior. The nucleation and growth of nanocrystals in FCZ glass-ceramics was investigated with in situ transmission electron microscopy heating experiments. The experiments showed the nucleation and growth of previously unreported BaF 2 nanocrystals in addition to the expected BaCl 2 nanocrystals. Chemical analysis of the BaF 2 nanocrystals shows an association with the optically active dopant previously thought only to interact with BaCl 2 nanocrystals. The association of the dopant with BaF 2 crystals suggests that it plays a role in the photoluminescent (PL) properties of FCZ glass-ceramics.

Optical properties of an indium doped CdSe nanocrystal: A density functional approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salini, K.; Mathew, Vincent, E-mail: vincent@cukerala.ac.in; Mathew, Thomas

2016-05-06

We have studied the electronic and optical properties of a CdSe nanocrystal doped with n-type impurity atom. First principle calculations of the CdSe nanocrystal based on the density functional theory (DFT), as implemented in the Vienna Ab Initio Simulation Package (VASP) was used in the calculations. We have introduced a single Indium impurity atom into CdSe nanocrystal with 1.3 nm diameter. Nanocrystal surface dangling bonds are passivated with hydrogen atom. The band-structure, density of states and absorption spectra of the doped and undopted nanocrystals were discussed. Inclusion of the n-type impurity atom introduces an additional electron in conduction band, and significantlymore » alters the electronic and optical properties of undoped CdSe nanocrystal. Indium doped CdSe nannocrystal have potential applications in optoelectronic devices.« less

Up-conversion luminescence properties and energy transfer of Tm{sup 3+}/Yb{sup 3+} co-doped BaLa{sub 2}ZnO{sub 5}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jing; Mei, Lefu, E-mail: mlf@cugb.edu.cn; Deng, Junru

2015-11-15

Tm{sup 3+}/Yb{sup 3+} co-doped BaLa{sub 2}ZnO{sub 5} up-conversion (UC) phosphors were successfully synthesized by high temperature solid-state reaction method. The X-ray diffraction (XRD) results show that synthesized phosphor co-doped with 0.75% Tm/10% Yb has the optimum pure phase of BaLa{sub 2}ZnO{sub 5} among different co-doping concentrations. The structure of BaLa{sub 2}ZnO{sub 5}:0.75% Tm/10% Yb phosphor was refined by the Rietveld method and results show the decreased unit cell parameters and cell volume after doping Tm{sup 3+}/Yb{sup 3+}, indicating that Tm{sup 3+}/Yb{sup 3+} have successfully replaced La{sup 3+}. Under excitation at 980 nm, Tm{sup 3+}/Yb{sup 3+} co-doped BaLa{sub 2}ZnO{sub 5} phosphorsmore » present bright blue emission near 478 nm generated by the {sup 1}G{sub 4}→{sup 3}H{sub 6} transition and weak red emissions around 653 nm and 692 nm generated by the {sup 1}G{sub 4}→{sup 3}F{sub 4} and {sup 3}F{sub 3}→{sup 3}H{sub 6} transitions of Tm{sup 3+}, respectively. The UC luminescence properties of BaLa{sub 2}ZnO{sub 5} phosphors co-doped with different Tm{sup 3+}/Yb{sup 3+} concentrations were investigated, and the related UC mechanisms of Tm{sup 3+}/Yb{sup 3+} co-doped BaLa{sub 2}ZnO{sub 5} depending on pump power were studied in detail. - Graphical abstract: Up-conversion luminescence of BaLa{sub 2}ZnO{sub 5}:Tm{sup 3+}/Yb{sup 3+} and its crystal structure and up-conversion mechanisms. - Highlights: • Up-conversion phosphors BaLa{sub 2}ZnO{sub 5} co-doped with Tm{sup 3+}/Yb{sup 3+} were synthesized by high temperature solid-state reaction method. • The crystal structure of BaLa{sub 2}ZnO{sub 5} and the changes of cell parameters and volume of BaLa{sub 2}ZnO{sub 5} after doping Tm{sup 3+} and Yb{sup 3+} have been discussed. • Up-conversion luminescence properties and energy transfer between Tm{sup 3+} and Yb{sup 3+} in BaLa{sub 2}ZnO{sub 5} have been discussed in detail.« less

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties

NASA Astrophysics Data System (ADS)

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-01

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities. Electronic supplementary information (ESI) available: Synthesis and TEM images of pure ZnO nanocrystals. Photocatalytic testing procedures and degradation curves. SEM and TEM images, SAED pattern and EDS spectra and maps of parts of Cu-ZnO hybrid samples. A schematic image of coincident lattice matching between Cu and ZnO. STEM-EDS elemental maps and XRD pattern of the Cu@CuNi-ZnO sample. Comparative synthetic parameters. See DOI: 10.1039/c6nr02055k

Nonvolatile memory with Co-SiO2 core-shell nanocrystals as charge storage nodes in floating gate

NASA Astrophysics Data System (ADS)

Liu, Hai; Ferrer, Domingo A.; Ferdousi, Fahmida; Banerjee, Sanjay K.

2009-11-01

In this letter, we reported nanocrystal floating gate memory with Co-SiO2 core-shell nanocrystal charge storage nodes. By using a water-in-oil microemulsion scheme, Co-SiO2 core-shell nanocrystals were synthesized and closely packed to achieve high density matrix in the floating gate without aggregation. The insulator shell also can help to increase the thermal stability of the nanocrystal metal core during the fabrication process to improve memory performance.

Cellulose nanocrystals: synthesis, functional properties, and applications

PubMed Central

George, Johnsy; Sabapathi, SN

2015-01-01

Cellulose nanocrystals are unique nanomaterials derived from the most abundant and almost inexhaustible natural polymer, cellulose. These nanomaterials have received significant interest due to their mechanical, optical, chemical, and rheological properties. Cellulose nanocrystals primarily obtained from naturally occurring cellulose fibers are biodegradable and renewable in nature and hence they serve as a sustainable and environmentally friendly material for most applications. These nanocrystals are basically hydrophilic in nature; however, they can be surface functionalized to meet various challenging requirements, such as the development of high-performance nanocomposites, using hydrophobic polymer matrices. Considering the ever-increasing interdisciplinary research being carried out on cellulose nanocrystals, this review aims to collate the knowledge available about the sources, chemical structure, and physical and chemical isolation procedures, as well as describes the mechanical, optical, and rheological properties, of cellulose nanocrystals. Innovative applications in diverse fields such as biomedical engineering, material sciences, electronics, catalysis, etc, wherein these cellulose nanocrystals can be used, are highlighted. PMID:26604715

Biopolymer coated gold nanocrystals prepared using the green chemistry approach and their shape-dependent catalytic and surface-enhanced Raman scattering properties.

PubMed

Chou, Chih-Wei; Hsieh, Hui-Hsuan; Hseu, You-Cheng; Chen, Ko-Shao; Wang, Gou-Jen; Chang, Hsien-Chang; Pan, Yong-Li; Wei, Yi-Syuan; Chang, Ko Hsin; Harn, Yeu-Wei

2013-07-21

This study deals with the preparation of multi-shaped nanoscale gold crystals under synthetically simple, green, and efficient conditions using a seed-mediated growth approach in the presence of hyaluronic acid (HA). These highly biocompatible multi-shaped gold nanocrystals were examined to evaluate their catalytic and surface enhanced Raman scattering (SERS) properties. The results show that the size and shape of the nanocrystals are mainly correlated to the amount of seed, seed size, HA concentration, and reaction temperature. Gold seeds accelerate the reduction of the gold precursor to form gold nanocrystals using HA. The HA serves as a reducing agent and a growth template for the reduction of Au(III) and nanocrystal stabilization. The multi-shaped gold nanocrystals showed superior catalytic properties and higher SERS performance. The simple, green approach efficiently controls the nanocrystals and creates many opportunities for future applications.

Atomic level characterization of cadmium selenide nanocrystal systems using atomic number contrast scanning transmission electron microscopy and Rutherford backscattering spectroscopy

NASA Astrophysics Data System (ADS)

McBride, James R.

This project involved the characterization of CdSe nanocrystals. Through the use of Atomic Number Contrast Scanning Transmission Electron Microscopy (Z-STEM) and Rutherford Backscattering Spectroscopy (RBS), atomic level structure and chemical information was obtained. Specifically, CdSe nanocrystals produced using a mixture of hexadecylamine (HDA) and trioctylphosphine oxide (TOPO) were determined to be spherical compared to nanocrystals produced in TOPO only, which had elongated (101) facets. Additionally, the first Z-STEM images of CdSe/ZnS core/shell nanocrystals were obtained. From these images, the growth mechanism of the ZnS shell was determined and the existence of non-fluorescent ZnS particles was confirmed. Through collaboration with Quantum Dot Corp., core/shell nanocrystals with near unity quantum yield were developed. These core/shell nanocrystals included a US intermediate layer to improve shell coverage.

Colloidal infrared reflective and transparent conductive aluminum-doped zinc oxide nanocrystals

DOEpatents

Buonsanti, Raffaella; Milliron, Delia J

2015-02-24

The present invention provides a method of preparing aluminum-doped zinc oxide (AZO) nanocrystals. In an exemplary embodiment, the method includes (1) injecting a precursor mixture of a zinc precursor, an aluminum precursor, an amine, and a fatty acid in a solution of a vicinal diol in a non-coordinating solvent, thereby resulting in a reaction mixture, (2) precipitating the nanocrystals from the reaction mixture, thereby resulting in a final precipitate, and (3) dissolving the final precipitate in an apolar solvent. The present invention also provides a dispersion. In an exemplary embodiment, the dispersion includes (1) nanocrystals that are well separated from each other, where the nanocrystals are coated with surfactants and (2) an apolar solvent where the nanocrystals are suspended in the apolar solvent. The present invention also provides a film. In an exemplary embodiment, the film includes (1) a substrate and (2) nanocrystals that are evenly distributed on the substrate.

Nanocrystal doped matrixes

DOEpatents

Parce, J. Wallace; Bernatis, Paul; Dubrow, Robert; Freeman, William P.; Gamoras, Joel; Kan, Shihai; Meisel, Andreas; Qian, Baixin; Whiteford, Jeffery A.; Ziebarth, Jonathan

2010-01-12

Matrixes doped with semiconductor nanocrystals are provided. In certain embodiments, the semiconductor nanocrystals have a size and composition such that they absorb or emit light at particular wavelengths. The nanocrystals can comprise ligands that allow for mixing with various matrix materials, including polymers, such that a minimal portion of light is scattered by the matrixes. The matrixes of the present invention can also be utilized in refractive index matching applications. In other embodiments, semiconductor nanocrystals are embedded within matrixes to form a nanocrystal density gradient, thereby creating an effective refractive index gradient. The matrixes of the present invention can also be used as filters and antireflective coatings on optical devices and as down-converting layers. Processes for producing matrixes comprising semiconductor nanocrystals are also provided. Nanostructures having high quantum efficiency, small size, and/or a narrow size distribution are also described, as are methods of producing indium phosphide nanostructures and core-shell nanostructures with Group II-VI shells.

Ferromagnetic cobalt nanocrystals achieved by soft annealing approach—From individual behavior to mesoscopic organized properties

NASA Astrophysics Data System (ADS)

Petit, C.; Wang, Z. L.; Pileni, M. P.

2007-05-01

By gentle annealing, 7 nm cobalt nanoparticles synthesized by soft chemistry, are transformed to hard magnetic hexagonal close packed (HCP) cobalt nanocrystals without changing the size, size distribution and passivating layer. This method permits to recover the nanocrystals isolated in solution after the annealing process and then to study the magnetic properties of the HCP cobalt nanocrystals at isolated status or in a self-organized film. Monolayer self-assembly of the HCP cobalt nanocrystals is obtained, and due to the dipolar interaction, ferromagnetic behavior close to room temperature has been observed. The magnetic properties differ significantly due to the influence of the substrate on the annealing process. This different approach of the annealing process of nanocrystals is compared to the classical approach of annealing in which the nanocrystals are first deposited on a substrate and then annealed.

All-inorganic Germanium nanocrystal films by cationic ligand exchange

DOE PAGES

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

2016-01-21

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

Quantitative Analysis of Charge Injection and Discharging of Si Nanocrystals and Arrays by Electrostatic Force Microscopy

NASA Technical Reports Server (NTRS)

Bell, L. D.; Boer, E.; Ostraat, M.; Brongersma, M. L.; Flagan, R. C.; Atwater, H. A.

2000-01-01

NASA requirements for computing and memory for microspacecraft emphasize high density, low power, small size, and radiation hardness. The distributed nature of storage elements in nanocrystal floating-gate memories leads to intrinsic fault tolerance and radiation hardness. Conventional floating-gate non-volatile memories are more susceptible to radiation damage. Nanocrystal-based memories also offer the possibility of faster, lower power operation. In the pursuit of filling these requirements, the following tasks have been accomplished: (1) Si nanocrystal charging has been accomplished with conducting-tip AFM; (2) Both individual nanocrystals on an oxide surface and nanocrystals formed by implantation have been charged; (3) Discharging is consistent with tunneling through a field-lowered oxide barrier; (4) Modeling of the response of the AFM to trapped charge has allowed estimation of the quantity of trapped charge; and (5) Initial attempts to fabricate competitive nanocrystal non-volatile memories have been extremely successful.

Structure and transformation of tactoids in cellulose nanocrystal suspensions

NASA Astrophysics Data System (ADS)

Wang, Pei-Xi; Hamad, Wadood Y.; MacLachlan, Mark J.

2016-05-01

Cellulose nanocrystals obtained from natural sources are of great interest for many applications. In water, cellulose nanocrystals form a liquid crystalline phase whose hierarchical structure is retained in solid films after drying. Although tactoids, one of the most primitive components of liquid crystals, are thought to have a significant role in the evolution of this phase, they have evaded structural study of their internal organization. Here we report the capture of cellulose nanocrystal tactoids in a polymer matrix. This method allows us to visualize, for the first time, the arrangement of cellulose nanocrystals within individual tactoids by electron microscopy. Furthermore, we can follow the structural evolution of the liquid crystalline phase from tactoids to iridescent-layered films. Our insights into the early nucleation events of cellulose nanocrystals give important information about the growth of cholesteric liquid crystalline phases, especially for cellulose nanocrystals, and are crucial for preparing photonics-quality films.

Metal halide solid-state surface treatment for nanocrystal materials

DOEpatents

Luther, Joseph M.; Crisp, Ryan; Beard, Matthew C.

2016-04-26

Methods of treating nanocrystal and/or quantum dot devices are described. The methods include contacting the nanocrystals and/or quantum dots with a solution including metal ions and halogen ions, such that the solution displaces native ligands present on the surface of the nanocrystals and/or quantum dots via ligand exchange.