New microarchitectures of (Er,Yb):Lu2O3 nanocrystals embedded in PMMA: synthesis, structural characterization, and luminescent properties
© Galceran et al.; licensee Springer. 2013
Received: 28 May 2013
Accepted: 3 August 2013
Published: 13 September 2013
KeywordsHybrid composite Polymer Nanocrystals Sesquioxide Erbium Ytterbium
In recent years, low-dimensional nanostructured materials based on porous templates have attracted considerable attention due to their potential applications in various kinds of functional devices [1–4]. Depositing specific materials onto porous templates creates ordered or disordered structures with suitable dimensions and periodicity and inverse replicas of the pores, thus allowing the expansion of these materials' possible application.
Porous silicon was discovered by Uhlir (in 1956) and was intensively investigated because of its excellent mechanical and thermal properties , its obvious compatibility with silicon-based microelectronics, and its low-cost fabrication . It was found to be a very promising and attractive candidate for use as a template because it can be fabricated with high precision and uniformity on a large scale. The porosity and average pore size and depth can be tuned by adjusting the electrochemical preparation techniques [7–10]. Depositing specific materials, such as polymers and nonlinear materials, into porous templates allows new structures to be tailored . Organic materials such as polymers are favored in many applications because many of these are optically transparent, biocompatible, and/or biodegradable. In addition, polymer devices are inexpensive and disposable. The air holes of porous silicon structures can be infiltrated with these advantageous polymers.
Nanocrystalline materials are generally defined as crystalline solids with grain sizes below 100 nm. The study and synthesis of nanocrystalline materials have been major research interests in recent years due to expectations of finding new or improved optical, electronic, and structural properties related to the nanoscale of materials .
The Pechini method is an alternative to the conventional sol–gel method for synthesizing nanocrystals. This chemical route is highly feasible and offers several advantages over conventional techniques, such as lower temperature requirements, lower cost, and greater simplicity .
One goal of our research is to make erbium-doped materials that emit light. As a host for erbium, the cubic RE2O3 (rare earths) are known as excellent optical materials because of their optimal thermal and spectroscopic properties . Efficiency in erbium emissions can be improved by co-doping with ytterbium, thus assuring a high absorption at 980 nm, where high-power diode lasers are commercially available. This class of composite materials has already been reported for planar optical amplifiers . Furthermore, the Er-Yb couple is well known for its up-conversion mechanisms, converting infrared (IR) light o visible light . The green and red emissions achieved by excitation in IR light or higher energies in erbium samples open up the possibility of using these composites as up-converters or down-converters for both solar cell and lighting applications.
In the present work, we describe a new template-based method for fabricating polymeric micro- and nanostructures. This method entails vacuum infiltration of a poly(methyl)methacrylate (PMMA) solution with embedded luminescent nanocrystals into the pores of a silicon template. The nanocrystals have been synthesized using the modified Pechini method. This method should be applicable to any polymer that can be dissolved in a solvent that is compatible with these template membranes.
Synthesis of nanocrystals
(Er,Yb):Lu2O3 nanocrystals were synthesized using the modified Pechini method, as described in our previous studies [17, 18]. The starting materials were Er2O3 (99.9%; Sigma-Aldrich Corporation, St. Louis, MO, USA), Yb2O3 (99.999%, Sigma-Aldrich Corporation) and Lu2O3 (99.9999%, METALL Rare Earth Limited, Shenzhen, China), and these were mixed to obtain stoichiometric products of 25 at.% Er and 25 at.% Yb:Lu2O3. To synthesize the nanocrystals, rare-earth oxides were first converted to nitrates by dissolving them with HNO3 (65%; Merck AG, Darmstadt, Germany) under stirring and heating. Ethylenediaminetetraacetic acid (EDTA) was then added, taking into account the molar ratio CM = (EDTA / Metal) = 1, and a solution of metal-EDTA complexes was obtained. Ethylene glycol (EG) was subsequently added to the solution with a molar ratio of CE = (EDTA / EG) = 2, and the precursor resin was formed through the esterification reaction while the solution was heated to about 363 K. Finally, the viscous gel obtained was calcinated at 1,073 K in air atmosphere to obtain the (Er,Yb):Lu2O3 nanocrystals. The CM ratio, CE ratio, and calcination temperature were already optimized in a previous study.
Synthesis of PMMA microcolumns
X-ray diffraction measurements were performed using a Bruker-AXS D8-Discover (Karlsruhe, Germany) diffractometer with a parallel incident beam (Göbel mirror) and a vertical goniometer, with a 0.02° receiving slit and a scintillation counter as a detector. A 30 × 30 cm2 general area diffraction system with a 1,024 × 1,024 pixel CCD detector was used for the micro-X-ray diffraction (μXRD) analysis, and an X-ray collimator system was used to analyze areas of 500 μm. CuKα radiation was obtained from a copper X-ray tube operated at 40 kV and 40 mA. Data were collected with an angular step of 0.02° at 900 s/frame per step. FULLPROF software based on the Rietveld method was used to refine the unit cell parameters [22, 23]. The particle size was estimated using Scherrer's equation and assuming spherical particles .
The chemical composition of the nanocrystals was examined by electron probe microanalysis (EPMA) in a Cameca SX50 (Gennevilliers Cedex, France) microprobe analyzer operating in wavelength-dispersive mode. The contents of erbium, ytterbium, and lutetium were measured using Lα and LiF as analyzing crystals.
A FEI QUANTA 600 (Hillsboro, OR, USA) environmental scanning electronic microscope (ESEM) and a JEOL JEM-1011 transmission electron microscope (TEM) with MegaView III (Soft Imaging System, Olympus, Tokyo, Japan) were used to study particle homogeneity, morphology, and size dispersion. To examine the samples by TEM, the nanocrystals were dispersed in acetone. Ultrasonication was used to reduce and disperse the agglomerates. They were then drop-cast onto a copper grid covered by a porous carbon film.
Cathodoluminescence (CL) experiments were performed at room temperature using Gatan MonoCL3+ system attached on Schottky-type field-emission scanning electron microscope (S4300SE Hitachi, Tokyo, Japan). The CL signal was dispersed by a 1,200-lines/mm grating blazed at 500 nm, and CL spectra and images were recorded using a Peltier-cooled Hamamatsu R943-02 photomultipler tube.
Results and discussion
Unit cell parameters of (Er,Yb):Lu 2 O 3 nanocrystals and of undoped Lu 2 O 3 , Er 2 O 3 , and Yb 2 O 3 as reference
Active ion (at.%)
Particle size (nm)b
Lu0.990 Er0.520 Yb0.490O3
Particle size and dispersion
Visualization of PMMA microcolumns by electron microscopy
As in the work of Yang et al. , the electron penetration depth, Lp, can be estimated using the expression Lp = 250 (MW / ρ)(E/Z1/2)n, where n = 1.2(1 to 0.29 log10Z), MW is the molecular weight of the material, ρ is the bulk density, Z is the atomic number, and E is the accelerating voltage (kV). The deeper the electrons penetrate the phosphor, the greater the increase in the electron-solid interaction volume and consequently in the quantity of Ln3+ excited ions. Using this approach, our penetration depth was estimated to be about 18 μm. This would correspond to the total height of the PMMA microcolumns.
Four manifolds were mainly observed, and these correspond to the following electronic transitions: 4G11/2 → 4I15/2 (violet emission centered on 380 nm), 2H9/2 → 4I15/2 (blue emission centered around 410 nm), 4S3/2 → 4I15/2 (green emission centered on 560 nm), and finally 4F9/2 → 4I15/2 (red emission centered on 680 nm). Broad band emission acting as a background is observed centered around 400 nm. A similar broad band which has been attributed to radiative recombination at defect centers has been also detected by cathodoluminescence in previous works [30, 31]. It could be observed that the intensity of the peaks decreases when the nanocrystals are embedded in the polymer matrix; therefore, only the last two transitions can be observed in these spectra. This fact could be attributed to the less quantity of the optical active material and to some scattering in the PMMA columns as a result of their apparent roughness.
As reported in previous works [32, 33], the red emission (Er3+: 4F9/2 → 4I15/2) was observed to predominate over the green emission (Er3+: (2H11/2, 4S3/2) → 4I15/2). This has been related to a 4I11/2 → 4I13/2 large nonradiative relaxation rate with a 4F9/2 → 4I9/2 small nonradiative relaxation rate, and this relation with the large 4I11/2 → 4I13/2 nonradiative relaxation rate is attributed to the occurrence of an efficient cross energy transfer to the OH− surface group as a result of the good energy match.
Furthermore, it was proposed that a cross-relaxation process was responsible for populating the 4F9/2 level and that this occurs via two resonant transitions: 4F7/2 → 4F9/2 and 4F9/2 → 4I11/2. In fact, the cross-relaxation process becomes more efficient as the average distance between the doping ions decreases and, therefore, the Er3+ concentration increases, thus enhancing the red emission. Our samples possess a 25 at.% erbium concentration, which is higher than the concentrations reported in previous studies . This also agrees well with the results of Yang et al. , who observed the predominance of green emission and the absence of red emission in flower microcrystallites that had been low doped with 1 at.% Er:Lu2O3.
Furthermore, as it can be observed in Figure 8, there is a change on the blue/green/red emission ratio when the nanocrystals are embedded in the PMMA. This change could be related to a change in the up-conversion mechanism affected by the presence of the high-energy phonons of the polymer, favoring the red emission in relation to the green emission which has decreased and the blue emission which has totally disappeared.
Summary of CIE properties of (Er,Yb):Lu 2 O 3 nanocrystals and (Er,Yb):Lu 2 O 3 nanocrystals embedded in PMMA microcolumns
(Er,Yb):Lu2O3 nanocrystals embedded in PMMA
The modified Pechini method was successfully applied to obtain cubic nanocrystals of Lu0.990Er0.520Yb0.490O3. Scherrer's approach and electronic microscopy gave us an average size of about 15 to 30 nm with 44% dispersion size. The (Er,Yb):Lu2O3 nanocrystals were embedded in PMMA microcolumns prepared by vacuum infiltration. The PMMA columns solidified inside the micropores of a silicon matrix to form 2D disordered arrays. The embedded nanocrystals showed a high degree of crystallinity, and their cathodoluminescence properties were not altered by the polymer matrix. It is interesting to point out how the erbium red emission, with its dominant wavelength of 642 nm, its CIE coordinates (0.72, 0.28), and its high color saturation, predominates over the visible emission. This is attributed to the high erbium concentration present in the samples.
This work was supported by the Spanish government through the projects MAT2011-29255-C02-02, TEC2010-21574-C02-02, PI09/90527, TEC2012-34397, HOPE CSD2007-00007 (Consolider-Ingenio 2010), and AECID-A/024560/09 and by the Catalan government through projects 2009SGR235 and 2009SGR549. Fabian Rotermund was supported by NRF grants (2011-0017494 and 2008-0061906) funded by the Korean government.
- Steinhart M, Wendorff JH, Greiner A, Wehrspohn RB, Nielsch K, Schilling J, Choi J, Gösele U: Polymer nanotubes by wetting of ordered porous templates. Science 2002, 296: 1997–1997. 10.1126/science.1071210View ArticleGoogle Scholar
- Kriha O, Zhao L, Pippel E, Gösele U, Wehrspohn RB, Wendorff JH, Steinhart M, Greiner A: Organic tube/rod hybrid nanofibers with adjustable segment length by bidirectional template wetting. Adv Funct Mater 2007, 17: 1327–1332. 10.1002/adfm.200601021View ArticleGoogle Scholar
- Grimm S, Schwirn K, Göring P, Knoll H, Miclea PT, Greiner A, Wendorff JH, Wehrspohn RB, Gösele U, Steinhart M: Non-destructive mechanical release of ordered polymer microfiber arrays from porous templates. Small 2007, 3: 993–1000. 10.1002/smll.200600544View ArticleGoogle Scholar
- Chen X, Steinhart M, Hess C, Gösele U: Ordered arrays of mesoporous microrods from recyclable macroporous silicon templates. Adv Mater 2006, 18: 2153–2156. 10.1002/adma.200600365View ArticleGoogle Scholar
- Ulhir A: Electrolytic shaping of germanium and silicon. Bell Syst Tech J 1956, 35: 333–347. 10.1002/j.1538-7305.1956.tb02385.xView ArticleGoogle Scholar
- Hirschman KD, Tsybeskov L, Duttagupta SP, Fauchet PM: Silicon-based visible light-emitting devices integrated into microelectronic circuits. Nature 1996, 384: 338–341. 10.1038/384338a0View ArticleGoogle Scholar
- Smith RL, Collins SD: Porous silicon formation mechanisms. J Appl Phys 1992, 71: 1–6. 10.1063/1.350737View ArticleGoogle Scholar
- Hamilton B: Porous silicon. Semicond Sci Technol 1995, 10: 1187–1207. 10.1088/0268-1242/10/9/001View ArticleGoogle Scholar
- Bettotti P, Dal Negro L, Gaburro Z, Pavesi L, Lui A, Galli M, Patrini M, Marabelli F: P-type macroporous silicon for two-dimensional photonic crystals. J Appl Phys 2002, 92: 6966–6972. 10.1063/1.1515127View ArticleGoogle Scholar
- Li YY, Cunin F, Link JR, Gao T, Betts RE, Reiver SH, Chin V, Bhatia SN, Sailor MJ: Polymer replicas of photonic porous silicon for sensing and drug delivery applications. Science 2003, 299: 2045–2047. 10.1126/science.1081298View ArticleGoogle Scholar
- Peña A, Di Finizio S, Trifonov T, Carvajal JJ, Aguiló M, Pallarés J, Rodriguez A, Alcubilla R, Marsal LF, Díaz F, Martorell J: A two-dimensional KTiOPO4 photonic crystal grown using a macroporous silicon template. Adv Mater 2006, 18: 2220–2225. 10.1002/adma.200502566View ArticleGoogle Scholar
- Gleiter H: Nanocrystalline materials. Prog Mater Sci 1989, 33: 223–230. 10.1016/0079-6425(89)90001-7View ArticleGoogle Scholar
- Pechini MP: Method of preparing lead and alkaline earth titanates and niobates and casting methods using the same to form a capacitor. 1967. US Patent 3.330.697Google Scholar
- Klein PH, Croft W: Thermal conductivity, diffusivity and expansion of Y2O3, Y3Al5O12 and LaF3 in the range of 77–300 K. J Appl Phys 1967, 38: 1603–1067. 10.1063/1.1709730View ArticleGoogle Scholar
- Wang J, Hu J, Tang D, Liu X, Zhen Z: Oleic acid (OA)-modified LaF3:Er, Yb nanocrystals and their polymer hybrid materials for potential optical-amplification applications. J Mater Chem 2007, 17: 1597–1601. 10.1039/b617754aView ArticleGoogle Scholar
- Auzel F: Upconversion and anti-stokes processes with f and d ions in solids. Chem Rev 2004, 104: 139–174. 10.1021/cr020357gView ArticleGoogle Scholar
- Galceran M, Pujol MC, Aguiló M, Díaz F: Sol–gel modified Pechini method for obtaining nanocrystalline KRE(WO4)2 (RE = Gd and Yb). J Sol–gel Sci Technol 2007, 42: 79–88. 10.1007/s10971-006-1517-3View ArticleGoogle Scholar
- Galceran M, Pujol MC, Aguiló M, Díaz F: Synthesis and characterization of nanocrystalline Yb:Lu2O3 by modified Pechini method. Mater Sci Eng 2008, 146: 7–15. 10.1016/j.mseb.2007.07.038View ArticleGoogle Scholar
- Lehmann V, Föll H: Formation mechanism and properties of electrochemically etched trenches n-type silicon. J Electrochem Soc 1990, 137: 653–659. 10.1149/1.2086525View ArticleGoogle Scholar
- Trifonov T, Marsal LF, Rodriguez A, Pallares J, Alcubilla R: Fabrication of two- and three-dimensional photonic crystals by electrochemical etching of silicon. Phys Status Solidi C 2005, 2: 3104–3107. 10.1002/pssc.200460743View ArticleGoogle Scholar
- Marsal LF, Formentín P, Palacios R, Trifonov T, Ferré-Borrull J, Rodriguez A, Pallarés J, Alcubilla R: Polymer microfibres obtained using porous silicon templates. Phys Status Solidi A 2008, 205: 2437–2440. 10.1002/pssa.200723556View ArticleGoogle Scholar
- Rodriguez-Carvajal J: Reference Guide for the Computer Program Fullprof. Saclay, France: Laboratorie León Brillouin. CEA-CNRS; 2000.Google Scholar
- Rietveld HM: A profile refinement method for nuclear and magnetic structures. J Appl Crystallogr 1969, 2: 65–71. 10.1107/S0021889869006558View ArticleGoogle Scholar
- Cullity BD: Element of X-Ray Diffraction. New York: Addison-Wesley; 1978.Google Scholar
- Shannon RD: Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 1976, 32: 751–767. 10.1107/S0567739476001551View ArticleGoogle Scholar
- Söderlund J, Kiss LB, Niklasson GA, Granqvist CG: Lognormal size distributions in particle growth processes without coagulation. Phys Rev Lett 1998, 80: 2386–2388. 10.1103/PhysRevLett.80.2386View ArticleGoogle Scholar
- Granqvist CG, Buhrman RA: Ultrafine metal particles. J Appl Phys 1976, 47: 2200–2220. 10.1063/1.322870View ArticleGoogle Scholar
- Donnay JDH, Harker D: A new law of crystal morphology extending the Law of Bravais. Am Mineral 1937, 22: 446–467.Google Scholar
- Yang J, Li C, Quan Z, Zhang C, Yang P, Li Y, Yu C, Lin J: Self-assembled 3D flowerlike Lu2O3 and Lu2O3:Ln3+ (Ln = Eu, Tb, Dy, Pr, Sm, Er, Ho, Tm) microarchitectures: ethylene glycol-mediated hydrothermal synthesis and luminescent properties. J Phys Chemy C 2008, 112: 12777–12785. 10.1021/jp803945wView ArticleGoogle Scholar
- Donegá CM, Zych E, Meijerink A: Luminescence of Lu2O3:Tm3+ nanoparticles. Mater Res Soc Symp Proc 2001, 667: G4.4.1-G4.4.6.View ArticleGoogle Scholar
- Müller HD, Schneider J, Lüth H, Strümpler R: Cathodoluminescence study of erbium in La1−xEr x F3 epitaxial layers on Si(111). Appl Phys Lett 1990, 57: 2422–2424. 10.1063/1.104177View ArticleGoogle Scholar
- Li Y, Zhang J, Zhang X, Luo Y, Ren X, Zhao H, Wang X, Sun L, Yan C: Near-infrared to visible upconversion in Er3+ and Yb3+ codoped Lu2O3 nanocrystals: enhanced Red color upconversion and three-photon process in green color upconversion. J Phys Chem C 2009, 113: 4413–4418. 10.1021/jp810275tView ArticleGoogle Scholar
- Vetrone F, Boyer JC, Capobianco JA, Speghini A, Bettinelli M: Concentration-dependent near-infrared to visible upconversion in nanocrystalline and bulk Y2O3:Er3+. Chem Mater 2003, 15: 2737–2743. 10.1021/cm0301930View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.