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Enhancing the Photoluminescence of Polymer-Stabilized CdSe/CdS/ZnS Core/Shell/Shell and CdSe/ZnS Core/Shell Quantum Dots in Water through a Chemical-Activation Approach
Mingfeng Wang, Meng Zhang, Jieshu Qian, Fei Zhao, Lei Shen, Gregory D. Scholes,* and Mitchell A. Winnik*
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, M5S 3H6 Ontario, Canada. Current address: Department of Chemistry and Biochemistry, University of California at Santa Barbara. Current address: Department of Chemistry, University of Minnesota Received February 18, 2009. Revised Manuscript Received July 10, 2009
We report a method for preparing highly photoluminescent, water-soluble CdSe/CdS/ZnS core/shell/shell and CdSe/ ZnS core/shell quantum dots (QDs) colloidally stabilized by double hydrophilic copolymers. The polymers, either a diblock copolymer poly(ethylene glycol-b-2-N,N-dimethylaminoethyl methacrylate) (PEG-b-PDMA) or a statistical copolymer poly(oligoethylene glycol methacrylate-co-2-N,N-dimethylaminoethyl methacrylate) (POEG-co-PDMA), were able to replace the hexadecylamine (HDA) or trioctylphosphine oxide (TOPO) ligands on the surface of the assynthesized QDs and impart water-solubility and colloidal stability to the QD nanocrystals. In water, the [CdSe/ZnS]/ POEG-co-PDMA colloids were present in the form of aggregates with a mean apparent hydrodynamic radius Rh of 54 nm and a narrow size distribution. Although the photoluminescence (PL) quantum yield (QY) of the polymer-treated QDs decreased upon transfer from an organic medium to water, much of this loss in brightness could be restored by the addition to the solution of an excess of a water-soluble primary amine such as 3-amino-propanol (APP). This chemicalactivation strategy of adding primary amines as PL activators to polymer-stabilized QDs did not lead to a spectral shift of either the absorption or emission of the QDs in water.
Introduction
Colloidal semiconductor nanocrystals, also called quantum dots (QDs), have emerged as unique luminescent materials for a variety of applications such as photonic devices,1,2 solar cells,3 and biological labeling.4-7 These QDs benefit from their narrow and symmetric emission, broad and continuous absorption, and remarkable stability against photobleaching. In addition, the optical and physical properties of QDs can be tuned by manipulating several factors, e.g., composition, size, shape, and surface chemistry. High-quality colloidal QDs, such as CdSe and related core-shell QDs, are normally synthesized via an organometallic approach involving hightemperature thermolysis of precursors.8-10 The surfaces of the resulting QDs are capped with hydrophobic organic ligands, typically consisting of medium length to long alkyl chains. The materials obtained form well-defined colloidal solutions in nonpolar solvents like hexane and toluene, as well as in semipolar solvents like
*Corresponding author. E-mail: gscholes@chem.utoronto.ca (G.D.S.); mwinnik@chem.utoronto.ca (M.A.W.).
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tetrahydrofuran, but are insoluble in polar solvents such as alcohols and water. For many applications, such as waterborne inks and coatings as well as for biological applications, the QDs must be rendered compatible with aqueous media. This can be accomplished in a number of ways, for example by encapsulating QDs or QD clusters with surfactants, phospholipids,11-14 or amphiphilic polymers18 or by incorporating QDs into colloidal hydrogels.19,20 Alternatively, the surface can be modified with hydrophilic molecules, for example, by ligand exchange. One can employ functional small
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molecules for this purpose,4-7,15 or polymers with ligands as pendant groups.22-26 Other criteria are also important. These include high photoluminescence (PL) quantum efficiency for the QDs, long-term colloidal stability and chemical stability in aqueous media, and for cell labeling experiments, biocompatibility. Many of these issues are discussed in a recent review of polymerquantum dot architectures.21 Despite significant progress on surface modification to prepare water-compatible QDs,4-7,11,12,14,16,17,22-26 it is still a challenge to satisfy all of the essential conditions in a single QD system. A common problem in transferring QDs originally synthesized with hydrophobic surface ligands from organic media to water is a substantial decrease in the PL quantum efficiency. This problem is particularly severe for CdSe QDs. Core-shell QDs such as ZnScoated CdSe (CdSe/ZnS) QDs are less susceptible than CdSe QDs to this strong decrease in PL intensity.10,27,28 Nevertheless, most of the reported procedures for dispersing core/shell QDs into water still lead to an inevitable decrease in the PL quantum yield.23,29-32 One approach to enhancing the brightness of QDs in solution is through photoactivation.27-38 The brightening achieved in this way was always accompanied by a noticeable blue shift of the absorption and PL spectra. This spectral shift has been attributed to the photooxidation of the QD surface, which leads to a decrease in the particle size. On the other hand, several research groups28,39-41 have reported that the addition of n-alkylamines to as-synthesized CdSe QDs dispersed in nonpolar solvents such as toluene and chloroform can increase the PL quantum efficiency. As Bullen and Mulvaney40 point out, these effects can be rather subtle. The magnitude of this effect depends upon the concentration and the molecular structure of the alkylamines, the solvent, and the history of the sample prior to addition of the amines. For example, Munro et al.28 reported that the exposure of as-synthesized CdSe QDs to a relatively low amount of n-butylamine led to an increase of the QD PL intensity, whereas an inverse effect, accompanied by a blue shift of QDs peak position, was observed when the concentration of n-butylamine was relatively high. This amineconcentration-dependent PL enhancement and quenching involved two competing interactions between the butylamine and the nanocrystals. Initially, the butylamine passivated surface sites, leading to PL enhancement. Subsequently, at a relatively high concentration of butylamine, etching of the QD surface became dominant, leading to
(26) Wang, M.; Felorzabihi, N.; Guerin, G.; Haley, J. C.; Scholes, G. D.; Winnik, M. A. Macromolecules 2007, 40, 63776384. (27) Guo, W. H.; Li, J. J.; Wang, Y. A.; Peng, X. G. J. Am. Chem. Soc. 2003, 125, 39013909. (28) Munro, A. M.; Plante, I. J. L.; Ng, M. S.; Ginger, D. S. J. Phys. Chem. C 2007, 111, 62206227. (29) Duan, H. W.; Nie, S. M. J. Am. Chem. Soc. 2007, 129, 33333338. (30) Nikolic, M. S.; Krack, M.; Aleksandrovic, V.; Kornowski, A.; Forster, S.; Weller, H. Angew. Chem. Intern. Ed. 2006, 45, 65776580. (31) Smith, A. M.; Duan, H. W.; Rhyner, M. N.; Ruan, G.; Nie, S. M. Phys. Chem. Chem. Phys. 2006, 8, 38953903. (32) Uyeda, H. T.; Medintz, I. L.; Jaiswal, J. K.; Simon, S. M.; Mattoussi, H. J. Am. Chem. Soc. 2005, 127, 38703878. (33) Cordero, S. R.; Carson, P. J.; Estabrook, R. A.; Strouse, G. F.; Buratto, S. K. J. Phys. Chem. B 2000, 104, 1213712142. (34) van Sark, W.; Frederix, P.; Van den Heuvel, D. J.; Gerritsen, H. C.; Bol, A. A.; van Lingen, J. N. J.; Donega, C. D.; Meijerink, A. J. Phys. Chem. B 2001, 105, 82818284. (35) Manna, L.; Scher, E. C.; Li, L. S.; Alivisatos, A. P. J. Am. Chem. Soc. 2002, 124, 71367145. (36) Jones, M.; Nedeljkovic, J.; Ellingson, R. J.; Nozik, A. J.; Rumbles, G. J. Phys. Chem. B 2003, 107, 1134611352. (37) Li, J. J.; Wang, Y. A.; Guo, W. Z.; Keay, J. C.; Mishima, T. D.; Johnson, M. B.; Peng, X. G. J. Am. Chem. Soc. 2003, 125, 1256712575. (38) Wang, Y.; Tang, Z. Y.; Correa-Duarte, M. A.; Pastoriza-Santos, I.; Giersig, M.; Kotov, N. A.; Liz-Marzan, L. M. J. Phys. Chem. B 2004, 108, 1546115469. (39) Talapin, D. V.; Rogach, A. L.; Kornowski, A.; Haase, M.; Weller, H. Nano Lett. 2001, 1, 207211. (40) Bullen, C.; Mulvaney, P. Langmuir 2006, 22, 30073013. (41) Kalyuzhny, G.; Murray, R. W. J. Phys. Chem. B 2005, 109, 70127021.
a decrease in the size of QD, accompanied by quenching of the PL and a blue shift of the emission peak wavelength. The experiments described above were focused primarily on CdSe QDs in nonpolar solvents. Here we are interested in coreshell nanocrystals, in which we examine a sample of CdSe/ZnS core/shell QDs as well as a sample of CdSe/CdS/ZnS core/shell/ shell QDs. The CdSe/CdS/ZnS core/shell/shell QDs we used were originally coated with hexadecylamine (HDA), and the CdSe/ZnS core/shell QDs with trioctylphosphine and trioctylphosphine oxide groups (collectively referred to as TOPO).10,39 Both of these materials exhibit much higher PL quantum yields and chemical stability than CdSe QDs. We were initially interested in finding conditions whereby a block copolymer poly(ethylene glycol-b-2N,N-dimethylaminoethyl methacrylate) (PEG-b-PDMA) and a copolymer of DMA and oligoethylene glycol-methacrylate (POEG-co-DMA) could carry these core-shell QDs into colloidally stable solutions in water. We based our experimental design on two previous findings that we have described previously. The first important observations was that PDMA can serve as a multidentate ligand for CdSe, and at ordinary temperatures, in solvents like toluene and tetrahydrofuran (THF) can displace TOPO from the surface of CdSe/TOPO QDs.22,24,26,42,43 This process has been studied in some detail, so that one has an idea of how many polymer chains bind to QDs of certain sizes,42 and how many DMA groups of the polymer participate in replacing each TOPO.43 These CdSe/PDMA QDs did not dissolve in water, however, in spite of the solubility of PDMA itself in cold water. The second key result was that multiple exchanges of CdSe/ TOPO QDs in THF with the sample of PEG-b-PDMA employed here provided stable aqueous solutions of individual CdSe/PEGb-PDMA QDs.26 Multiple exchanges led to enhanced displacement of residual TOPO groups from the QD surface. This, in conjunction with the enhanced hydrophilicity of the PEG component of the block copolymer, made the dispersion of these particles in water possible. Here we report that the oligoethylene glycol chains of POEG-co-DMA are effective in transferring core-shell QDs from THF into aqueous media, but the species obtained were not individual QDs. Rather, we find polymerstabilized QD hydrogels in which the QDs themselves appear to act as individual emitting species, but the ensemble is present in the form of clusters ca. 100 nm in diameter and with a narrow distribution of sizes. When we discovered that transfer of these core-shell QDs into water was accompanied by a significant decrease in the PL quantum yield, we then treated these solutions with varying quantities of water-soluble amines to see if some of the lost luminescence intensity could be recovered. Here we observed a remarkable enhancement, but only in the presence of rather high concentration of primary amines such as 3-amino-1-propanol. This chemical enhancement effect is also an important part of the story reported in this paper.
Experimental Section
Materials. 3-Amino-1-propanol (APP, 99+%), 3-(aminomethyl)pyridine (AMP, 99+%), 2-mercaptoethanol (MPE, 98%), imidazole (99%), and pyridine (99%) were purchased from Aldrich and used without further purification. Hexadecylamine-capped CdSe/CdS/ZnS core/shell/shell QDs44 and TOPO-coated CdSe/
(42) Wang, M.; Dykstra, T. E.; Lou, X.; Salvador, M. R.; Scholes, G. D.; Winnik, M. A. Angew. Chem., Int. Ed. 2006, 45, 22212224. (43) Shen, L.; Soong, R.; Wang, M.; Lee, A.; Wu, C.; Scholes, G. D.; Macdonald, P. M.; Winnik, M. A. J. Phys. Chem. B 2008, 112, 16261633. (44) Talapin D. V., Mekis I., Gotzinger S., Kornowski A., Benson O., Weller H. J. Phys. Chem. B. 2004, 108, 18826-18831.
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Article ZnS core/shell QDs10,39 were received as a gift from Evident Technologies. The QDs were purified by precipitation in methanol and redispersion in THF before use. PEG45-b-PDMA45 (Mn(NMR) = 9000, Mw/Mn(GPC) = 1.5) was synthesized by atom-transfer radical polymerization (ATRP) and is the same sample that we reported previously.26 POEG-co-PDMA (Mn = 7000, Mw/Mn = 3.1) was synthesized by conventional radical copolymerization of DMA and HO(CH2CH2O)6-methacrylate (M=338) in toluene at 70 C, initiated with AIBN. In more detail, DMA (1.500 g, 9.5 mmol), HO(CH2CH2O)6-methacrylate (1.500 g, 4.2 mmol), and toluene (50 mL) were added into a 100 mL Schlenck flask equipped with a magnetic stirrer bar and a water condenser. The mixture was bubbled with nitrogen under stirring for 30 min at room temperature. Then a toluene solution of AIBN (0.022 g, 0.1 mmol) was slowly added to the monomer mixture to start the polymerization at 70 C. The reaction was continued for 24 h, and the mixture was then added to excess hexane (300 mL) to precipitate the polymer. The resulting copolymer was purified by dissolving in THF followed by precipitating in hexane, and repeated for another two cycles. Finally, the polymer was dried in a vacuum oven at 40 C overnight. Yield: 1.8 g, 60%. Mn (GPC, THF/NEt3 2 vol % as the eluent, polystyrene standards) = 7000, Mw/Mn =3.1. The relative ratio of HO(CH2CH2O)6- to DMA in the final polymer product was 3:7 (by mole) which was determined by 1H NMR (see Figure S5 in the Supporting Information). Optical absorption spectra were measured at room temperature on a Perkin-Elmer Lambda 25 spectrometer using 1.00 cm quartz cuvettes. Photoluminescence spectra were measured using a SPEX Fluorolog-3 spectrofluorometer (Jobin Yvon/SPEX, Edison, New Jersey). The emission spectra were corrected using an algorithm built into the software. The PL QY of the CdSe/CdS/ ZnS and CdSe/ZnS QDs were measured using Rhodamine 6G (QY = 0.95) in absolute ethanol as a standard. Solutions of similar optical density (ca. 0.06) at the excitation wavelength (480 nm) were prepared for both QDs and Rhodamine 6G. Fluorescence spectra were recorded from 550 to 750 nm and integrated on a wavelength scale. Transmission electron microscopy (TEM) images were taken using a Hitachi HD2000 STEM instrument. Right-angle dynamic light scattering (DLS) measurements were carried out at 25.0 ( 0.05 C using an instrument from ALV described previously.48 Size information was obtained by analysis of the autocorrelation function decay by CONTIN,49 using software included with the ALV instrument. 3.3 10-2 M N(Me)2 groups) was dissolved in toluene (3 mL). [CdSe/CdS/ZnS]/HDA (0.1 mL, 10 mg/mL in toluene) was then added. The mixture was stirred overnight at room temperature. The mixture was concentrated to ca. 0.5 mL by removal of most of the solvent with a rotary evaporator. Hexane (ca. 8 mL) was then added to the mixture. Both the polymer and the ligand-exchanged CdSe/CdS/ZnS QDs precipitated as a viscous mixture. Sedimentation was rapid without centrifugation, and the supernatant was clear and colorless. The colorless supernatant was decanted, and the residue was redispersed in toluene (2 mL). This precipitation/redispersion process was repeated for three additional cycles. Then the sediment was dried under a N2 flow (or in vacuum) at room temperature. The dry solid obtained at this point could be dissolved (dispersed) in distilled water.
(45) Hohng, S.; Ha, T. J. Am. Chem. Soc. 2004, 126, 13241325. (46) Yu, W. W.; Qu, L. H.; Guo, W. Z.; Peng, X. G. Chem. Mater. 2003, 15, 28542860. (47) Li, R. F.; Lee, J.; Yang, B. C.; Horspool, D. N.; Aindow, M.; Papadimitrakopoulos, F. J. Am. Chem. Soc. 2005, 127, 25242532. (48) Guerin, G.; Raez, J.; Manners, I.; Winnik, M. A. Macromolecules 2005, 38, 78197827. (49) Provencher, S. W. Comput. Phys. Commun. 1982, 27, 213227.
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Effect of Small Ligands on the PL of [CdSe/CdS/ZnS]/ PEG-b-PDMA in Water. Aliquots of an aqueous dispersion
of [CdSe/CdS/ZnS]/PEG-b-PDMA (0.7 mL, optical density (A620 nm) = 0.06) were mixed with excess amounts (6.5 mmol each) of primary amines: 3-amino-1-propanol (0.5 mL), 2-mercaptoethanol (0.46 mL), or 3-(aminomethyl)-pyridine (0.64 mL). Water was then added to bring the total volume to 3.2 mL. Similar experiments were carried out by adding 6.5 mmol of pyridine (0.53 mL) or imidazole (0.45 g) to 0.5 mL of [CdSe/CdS/ZnS]/PEG-bPDMA (A620 nm = 0.06), and then adjusting the final volume to 2.5 mL with water. As a control, 0.5 mL of this [CdSe/CdS/ ZnS]/PEG-b-PDMA solution was diluted to 2.5 mL with water. All of the samples were stored for 3 days in the dark at room temperature before the PL measurements.
Photoactivation of [CdSe/CdS/ZnS]/PEG-b-PDMA in Water. An aqueous dispersion of [CdSe/CdS/ZnS]/PEG-bPDMA (3 mL, optical density A620 nm = 0.1) was placed in a fluorescence cell and irradiated in a Luzchem LZC-UV reactor with 8 overhead lamps. The irradiation wavelength of the UVA reactor was in the range 316-400 nm with a peak at 365 nm. The dose was 53 W m-2.
Effect of Ionic Strength on the PL of [CdSe/CdS/ZnS]/ PEG-b-PDMA in Water. The samples were prepared by
adding aqueous dispersions of [CdSe/CdS/ZnS]/PEG-b-PDMA (0.4 mL, A620 nm = 0.08) to NaCl solutions (1.8 mL) of different concentrations (0 to 1.5 M). For the sample at 0 M NaCl, 1.8 mL water was added to dilute the original [CdSe/CdS/ZnS]/PEG-bPDMA aqueous dispersion (0.4 mL).
Ligand Exchange of HDA-Coated CdSe/CdS/ZnS QDs with POEG-co-PDMA. POEG-co-PDMA (54 mg) was dissolved in 2 mL of THF/toluene (1:1, v/v). [CdSe/CdS/ZnS]/HDA (0.1 mL, 10 mg/mL in toluene) was then added. The mixture was dried by rotary evaporation and then redispersed into ca. 0.5 mL of THF. Then hexane (ca. 8 mL) was added to the mixture. Both the polymer and the ligand-exchanged CdSe/CdS/ZnS QDs precipitated as a viscous mixture. The supernatant was clear and colorless. The colorless supernatant was decanted, and the residue was redispersed in THF (2 mL). This precipitation/redispersion process was repeated for three additional cycles. The sediment was then dried under a N2 flow (or in vacuum) at room temperature. The dry solid obtained at this point could be dissolved (dispersed) in distilled water.
Ligand Exchange of TOPO-Coated CdSe/ZnS QDs with POEG-co-PDMA. [CdSe/ZnS]/TOPO (2.5 mL, 2 mg/mL in
THF) was added to a solution of POEG-co-PDMA (5 mL, 32 mg/ mL in THF). The mixture was stirred in the dark at room temperature for 3 days. The solution was then concentrated to 0.5 mL under a vacuum using a rotary evaporator. Hexane (ca. 8 mL) was added to the mixture under stirring. Both the polymer and the ligand-exchanged CdSe/ZnS QDs precipitated as a viscous mixture. The colorless supernatant was decanted. The residue was redispersed in THF (2 mL) and stirred for 8 h. This precipitation/redispersion process was repeated three times. Finally, the sediment was dried under N2 flow (or in vacuum) at room temperature, followed by dispersion in distilled water. [CdSe/ZnS]/POEG-co-PDMA samples for dynamic light scattering were prepared in a similar manner. A solution of [CdSe/ ZnS]/TOPO in THF (2 mL 2 mg/mL, THF) and POEG-coPDMA (4 mL 32 mg/mL, THF) were mixed and stirred in the dark for 3 days. Then it was concentrated and subjected to three precipitation and redispersion cycles as described above. Samples of this residue were dissolved (redispersed) in THF, methanol, and water.
Ligand Exchange of HDA-Coated CdSe/CdS/ZnS QDs with PEG-b-PDMA. PEG-b-PDMA (52 mg, containing
Effect of APP Concentration on the PL of [CdSe/ZnS]/ POEG-co-PDMA in Water. Aliquots of [CdSe/ZnS]/POEGco-PDMA water-dispersion (0.4 mL) were mixed with various amounts of deionized water (3.6 (as a control), 3.0, 2.4, 1.8, 1.2, 0.6 mL), followed by addition of desired amounts of APP (0 (as a
Langmuir 2009, 25(19), 1173211740
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Scheme 1. Molecular Structures of PEG-b-PDMA and POEG-coPDMA
Article
control), 0.6, 1.2, 1.8, 2.4, 3.0 mL, respectively). The final volume of each mixture was 4.0 mL. The concentration of APP in each mixture was 0, 2, 4, 6, 8, 10 M, respectively. All of the mixtures were stored for 4 days in the dark at room temperature before UV-vis absorption and PL measurements. Similar samples were prepared for DLS experiments.
PL Evolution of [CdSe/ZnS]/POEG-co-PDMA in Water in the Presence of APP. An aliquot (0.9 mL) of [CdSe/ZnS]/
POEG-co-PDMA aqueous dispersion was added to 0.6 mL APP. The optical density at 600 nm was adjusted to 0.02 by adding 1.4 mL deionized water to the mixture. The mixture was homogeneous and transparent after being gently shaken. Then it was transferred to a fluorescence cell (1 cm 1 cm) and stored in the dark at room temperature. PL measurements were conducted over time using a sealed solution of Rhodamine 6G in absolute ethanol as a standard.
Preparation and Optical Properties of PEG-b-PDMAStabilized CdSe/CdS/ZnS Core/Shell/Shell QDs. The CdSe/CdS/ZnS core/shell/shell QDs that we used in this study are stabilized by an organic layer consisting of hexadecylamine (HDA) molecules that serve as surface-passivating ligands. Figure 1a shows a TEM image of these HDA-coated QDs cast from a toluene solution. The average size of the nanoparticles is 5 ( 2 nm. The particle shapes include spheres, triangles, and polygons. Despite the relatively wide distribution of sizes and shapes, these core-shell QDs still form regular domains after drying on the TEM grid. An interesting phenomenon is that small QDs prefer to locate at the edges of the two-dimensional domains formed upon drying, whereas the larger ones are found in the interior. In the Introduction, we mentioned that in previous studies of the interaction of PEG-b-PDMA with CdSe/TOPO QDs, multiple exchanges involving repeated centrifugation/ redispersion cycles were necessary to achieve water solubility. We also found that QDs became soluble in water in a single step if the mixture of CdSe/TOPO QDs and block copolymer were subjected to sonication in a 60-W ultrasonic cleaning bath. While this worked well in accelerating the ligand exchange, the resulting quantum dots had a very weak PL intensity in water. Thus, for CdSe QDs, sonication is not a useful step in the preparation of photoluminescent QDs in water. With the idea that CdSe/CdS/ZnS core/shell/shell QDs might be more robust in resisting surface damage or surface oxidation upon exposure to ultrasonic waves, we repeated this experiment with our CdSe/CdS/ZnS QD sample. Although some ligand exchange took place, even 1 h of sonication was not sufficient for the product obtained to dissolve in water, following precipitation in hexane and drying. It is possible that HDA binds more strongly to ZnS than the binding of TOPO to CdSe. The multiple precipitation/redispersion process that we developed previously for CdSe/TOPO + PDMA-b-PEG also works very effectively to transfer the HDA-coated CdSe/CdS/ZnS core/ shell/shell QDs into water. Figure 1b shows a TEM image of PEG-b-PDMA-stabilized CdSe/CdS/ZnS core/shell/shell QDs obtained from an aqueous solution. The size and shape of the QDs in water did not change significantly compared to those of the original QDs in toluene. Although we do not have direct evidence on the state of aggregation (if any) for these blockcopolymer-stabilized QDs in water, the presence of single particles in the TEM image in Figure 1b suggests that aggregation is not dominant for these colloids in water, and that the small clusters seen in this image are formed upon drying. In ref 26, we reported that ligand exchange of CdSe/TOPO QDs with this same block copolymer sample led to unaggregated polymer-stabilized QDs in water. These species were characterized by DLS. The CONTIN plot showed a narrow distribution of species with a hydrodynamic radius Rh of 10 nm, a value consistent with polymer adsorption onto individual QD particles. Panels c and d in Figure 1 show the absorption and PL spectra, respectively, of the QDs before and after transfer into water. After the ligand exchange and the transfer from toluene to water, there was no shift of the band-edge absorbance, but a slight red-shift (4 nm) can be seen for the PL spectrum. The PL quantum yield (PL) of the original HDA-coated CdSe/CdS/ZnS core/shell/shell QDs in toluene was approximately 64%, which dropped to 16% for the polymer-stabilized QDs in water. PL = 0.16 is a respectrable value for QDs in aqueous media. Optical Stability of PEG-b-PDMA-Stabilized CdSe/ CdS/ZnS Core/Shell/Shell QDs in Water. We tested the sensitivity of these aqueous solutions to the presence of sodium chloride. Unlike polymer-stabilized CdSe QDs, where pronounced PL
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Figure 1. (a, b) Dark-field TEM images of HDA-coated CdSe/CdS/ZnS core/shell/shell QDs from(a) toluene and (b) the same QDs after ligand exchange with PEG-b-PDMA and transfer into water. (c) Absorption and (d) PL spectra of HDA-coated CdSe/CdS/ZnS core/shell/ shell QDs from toluene and [CdSe/CdS/ZnS ]/PEG-b-PDMA QDs in water.
quenching was observed,26 PEG-b-PDMA-stabilized CdSe/CdS/ ZnS core/shell/shell QDs were largely unaffected. Only a slight decrease was found for the band-edge emission intensity of the QDs at 640 nm over the range of 0 to 1.5 M NaCl (see Figure S1 in the Supporting Information). No trap-state emission was observed at longer wavelengths. The PL of the [CdSe/CdS/ZnS]/PEG-bPDMA core/shell/shell QDs was much less sensitive to exposure to UV irradiation than that of CdSe/PEG-b-PDMA.26 There was no shift of the PL spectrum for an aqueous solution of [CdSe/ CdS/ZnS]/PEG-b-PDMA under the irradiation of the sample with a 365 nm light source and only a slight increase (9%) of the PL intensity at 640 nm was observed after 1.5 h of irradiation (see Figure S2 in the Supporting Information). Luminescence Enhancement of [CdSe/CdS/ZnS]/PEGb-PDMA through Chemical Activation. Although the block copolymer is very effective at providing colloidal stability to CdSe/CdS/ZnS QDs, it is still disappointing that transfer to water is accompanied by a decrease in the PL QY. The decrease of the PL intensity of ligand-exchanged QDs after transfer to water is often attributed to the introduction of surface traps,27,31 and this intensity decrease is commonly observed in ligand exchange of core-shell QDs with other polymers followed by transfer into water.23,29,30,32 We noted with interest a recent report from the Papadimitrakopoulos group25 that replacement of TOPO ligands on CdSe/TOPO QDs in toluene by 3-amino-1-propanol (APP) led to an increase in the PL QY from 10 to 25% and provided colloidal stability in toluene-ethanol mixtures. Subsequent treatment with polyallylamine and transfer to water led to aqueous dispersions of QD-polymer clusters, with diameters in the range of 50 to 200 nm, and PL QY values as high as 20%. The literature results cited in the Introduction on the enhancement of CdSe/TOPO QD photoluminescence in the presence of primary amines28,39-41 makes it is likely that the primary amino groups of APP and the polyallylamine are serving a similar function here, providing enhanced passivation of surface trap
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sites through the density of ligand binding. Although this phenomenon is well-documented for CdSe QDs, we are unaware of any reports describing PL intensity enhancement by the addition of amines to solutions of core-shell QDs, particularly in water. To test whether amines are able to provide an increase in the quantum yields for core-shell QDs in water, we examined the effect of adding excess low-molar-mass amines to aqueous solutions of [CdSe/CdS/ZnS]/PEG-b-PDMA QDs. We imagined that these molecules could diffuse through the polymer corona, penetrate to the surface of CdSe/CdS/ZnS core/shell/shell QDs, and bind to vacant sites that remained from the ligand exchange with PEG-b-PDMA. The initial experiments were carried out with APP. Figure 2 shows the absorption and PL spectra of [CdSe/CdS/ZnS]/PEG-b-PDMA QDs in water before and after the addition of excess APP (6.5 mmol). APP has no detectable absorbance at 480 nm or any emission when illuminated at this wavelength. In this experiment, the concentration of QDs in the two solutions was the same. Although the absorption spectrum of the QDs did not change after the addition of APP, the PL intensity at 640 nm doubled. In addition, we note that the position and shape of the PL remained the same as before addition of APP. These solutions of [CdSe/CdS/ZnS]/PEGb-PDMA QDs in water in the presence of APP remained highly fluorescent and colloidally stable for more than 2 months when stored in the dark. In these experiments, we infer that the binding of the amine to the surface sites is not very strong. Excess amine is required to see this effect, and removal of the amine by dialysis against water was accompanied by a decrease in the PL intensity of the QDs. We then investigated how the molecular structure of small ligands affected the PL of [CdSe/CdS/ZnS]/PEG-b-PDMA QDs in water. For this purpose, the same excess amount (6.5 mmol) of other amines was added to aqueous dispersions of [CdSe/CdS/ ZnS]/PEG-b-PDMA QDs. We selected 3-(aminomethyl)pyridine (AMP), 2-mercaptoethanol (MPE), imidazole, and pyridine for investigation. In each instance, the final concentration of the QDs
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Figure 2. (a) Absorption and (b) PL spectra of [CdSe/CdS/ZnS]/ PEG-b-PDMA core/shell/shell QDs in water before and after addition of APP (6.5 mmol, CAPP = 2 M in the final solution).
Figure 3. Relative PL intensity of [CdSe/CdS/ZnS]/PEG-bPDMA QDs in water after addition of different molecules as possible activators. The PL intensity before addition of any activators was set as 1. The molecular structure of AMP, APP, and MPE are shown in the box. The estimated precision in the enhancement values is ( 10%.
was adjusted to the same value with water. Figure 3 shows the relative PL intensity (at 640 nm) of the samples in the presence of
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these various ligands, compared to that of the sample of the asprepared [CdSe/CdS/ZnS]/PEG-b-PDMA QDs in water. As in the case of APP, PL enhancement was observed for AMP. This effect is likely mainly due to the influence of the primary amine group because pyridine itself resulted only in a moderate increase in the QD PL intensity. In contrast, both 2-mercaptoethanol (MPE) and imidazole quenched the emission of these QDS, and MPE showed the strongest quenching effect. Quenching by thiols of the PL intensity of CdSe QDs has been reported by several research groups.28,30,41 This effect is normally attributed to the hole-trapping capacity of thiol groups on the surface of CdSe nanocrystals. This observation, however, is different from that of Hohng and Ha,45 who reported that low concentrations of MPE suppressed blinking of streptavidin-coated CdSe/ZnS QDs in tris-buffered saline solution. This was a transient effect that ended when the MPE was washed away. In the authors view, the thiol moiety, a potent electron donor, donates electrons to surface electron traps, rendering them incapable of accepting electrons from the QD, hence reducing the frequency of blinking. Ligand Exchange [CdSe /ZnS]/TOPO with POEG-coPDMA. In this section and the following section, we describe experiments in which the statistical copolymer of POEG-coPDMA was used as a dispersant for core/shell QDs. We first describe the interaction of this polymer with [CdSe/ZnS]/TOPO QDs, and begin by providing a brief characterization of the QDs themselves. Figure 4a shows a dark-field TEM image of these [CdSe/ZnS]/ TOPO QDs after being dried from toluene solution on a carboncoated grid. Size analysis gives an average diameter of 5.7 ( 0.8 nm for the inorganic core. This core/shell QD sample shows a band-edge absorbance at 605 nm (see below, Figure 5a), suggesting that the diameter of the CdSe core is 5.4 nm on average.46 These results imply that the thickness of the ZnS shell is around 0.15 nm. DLS measurements (not shown) show only a weak autocorrelation decay, consistent with the presence of very small particles and the absence of any aggregates. Thus the domains of regularly packed QDs in the middle part of the TEM image shown in Figure 4a must have formed as a consequence of solvent evaporation during the TEM sample preparation. When a solution of the [CdSe/ZnS]/TOPO QDs in toluene was treated with excess POEG-co-PDMA in THF, ligand exchange took place. After 4 cycles of precipitation with hexane followed by redispersion in THF, the QDs formed solutions in water. These solutions of [CdSe/ZnS]/POEG-co-PDMA remained colloidally stable after standing in the dark over 1 year under ambient conditions. Figure 4b shows a dark-field TEM image of [CdSe/ ZnS]/POEG-co-PDMA prepared from an aqueous solution. One can see that the QD particles themselves maintain their size and shape after being transferred into water. Unlike the image in Figure 1B, no individual nanoparticles can be seen here. This difference is an indirect indication that the QDs in aqueous solution may exist in the form of aggregates. The inset in Figure 4b shows dark spaces around each QD, which suggests that even in the aggregates, individual QDs are surrounded by polymer molecules. To test this idea, we carried out right-angle DLS measurements on solutions of [CdSe/ZnS]/POEG-co-PDMA in three different solvents. CONTIN plots are shown in Figure 4c, and the autocorrelation decay plots are shown as Figure S8 in Supporting Information. The CONTIN plots for the solution in THF is particularly informative. It shows a broad but monomodal distribution of species with an apparent mean hydrodynamic radius (Rh) of 11 nm. We learn that the solution consists primarily
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Figure 4. (a, b) Dark-field TEM images of TOPO-coated CdSe/ ZnS core/shell QDs from (a) toluene and (b) the same QDs after ligand exchange with POEG-co-PDMA and transfer into water. The insets show higher magnification images. (c) CONTIN plots for CdSe/ZnS ligand exchanged with POEG-co-PDMA and dispersed in water (Rh =54 nm), methanol (Rh =11 nm), and THF (Rh = 11 nm), respectively.
Figure 5. (a) Absorption and (b) PL spectra of CdSe/ZnS core/ shell QDs from toluene and the same QDs after ligand exchange with POEG-co-PDMA and transfer into water. (c) PL spectra of [CdSe/ZnS]/POEG-co-PDMA QDs in water in the presence of different amount of APP.
of individual polymer-coated QDs, accompanied by a distribution of aggregates with Rh values of tens of nanometers. By recalling that the scattering intensity increases with the sixth power of the radius, one can infer that band broadening is due to rather small amounts of larger aggregates. When the solution is transferred to methanol, the magnitude of Rh is unchanged, but one can see a longer tail due to scattering by even larger aggregates. We speculate that the aggregates are formed when the polymer-coated QDs and excess polymer were precipitated in hexane, allowing some polymer chains to form bridges by binding to the surface of more than one QD. In aqueous solution, we see a rather different behavior. As shown in Figure 5c, the colloidal solutions of [CdSe/ZnS]/POEGco-PDMA in water are characterized by a very narrow distribution of larger clusters, with Rh = 54 nm. The presence of welldefined hydrogel-like aggregates in water has similarities with the result of Papadimitrakopoulos and co-workers18 cited above.
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Although aggregation of the QDs in water can be rationalized in terms of extensive polymer bridging, it is still difficult to explain why we obtain such a narrow distribution of aggregate sizes. Panels a and b in Figure 5 compare the absorption and PL spectra, respectively, of [CdSe/ZnS]/TOPO in toluene and [CdSe/ ZnS]/POEG-co-PDMA in water. The absorption spectra appear rather similar for these two samples. In contrast, the PL QY of the QDs dropped from 24% in toluene to 3% after transfer into water, accompanied by a 4 nm red-shift of the maximum emission. Comparison of these results to those involving CdSe/CdS/ ZnS core/shell/shell QDs and POEG-co-PDMA (Figure 4) implies that the PL intensity of these CdSe/ZnS core/shell QDs is more susceptible to quenching in water than that of CdSe/CdS/ ZnS core/shell/shell QDs. Next we examined the optical properties of [CdSe/ZnS]/ POEG-co-PDMA in water in the presence of different amounts of APP. In this experiment, the concentration of the QDs
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Figure 6. Evolution of the (a) PL spectrum and (b) the maximum PL intensity of [CdSe/ZnS ]/POEG-co-PDMA QDs in water in the presence of 2.7 M APP.
(Abs605 nm = 0.02) was kept constant, whereas the concentration of APP (CAPP) was varied from 0 to 10 M. All of the samples were aged for 4 days in the dark at room temperature before making the optical measurements. There was no obvious wavelength-shift for the band-edge absorbance of the QDs at all of the APP concentrations that we examined (see Figure S4 in the Supporting Information). In contrast, different results were observed for the PL intensity. The change of the PL intensity was negligible when CAPP was lower than 2 M (data not shown), whereas the maximum PL intensity increased by 46% at CAPP = 2 M, by 100% at CAPP=8 M, and by 260% at CAPP =10 M (Figure 5c). Despite the significant change in the PL intensity, there was still no shift in the wavelength of the maximum PL. To get a better understanding of the kinetics of ligand exchange, we used an aqueous solution of [CdSe/ZnS]/POEG-coPDMA (Abs600 nm = 0.02) in the presence of 2.7 M APP to monitor the evolution of the QD PL upon addition of APP. Figure 6a shows the PL spectra of this sample over different aging periods. One can see that the maximum PL intensity of the QDs increased with the increase of aging time, whereas the wavelength of the maximum PL remained unchanged. The plot of the maximum PL intensity (at 620 nm) as a function of the aging time (Figure 6b) suggests that there was a sharp increase of the maximum PL intensity within the initial 4 h, followed by a relatively slow increase over the next 86 h. Another question we consider is whether the presence of APP leads to deaggregation of the [CdSe/ZnS]/POEG-co-PDMA clusters seen in Figure 4c. APP is an amino alcohol, and we saw little aggregation for the polymer-coated QDs in methanol. DLS experiments carried out in water in the presence of 2, 6, and 10 M APP all show a narrow distribution of aggregates. Autocorrelation decay and CONTIN plots are shown as Figures S6 and S7 in the Supporting Information. APP is much more viscous (APP = 31.5 mPa s) than water (H2O = 0.89 mPa s). Thus the
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Figure 7. (a) Dark-field TEM image of CdSe/CdS/ZnS core/shell/ shell QDs after ligand exchange with POEG-co-PDMA and transfer into water. (b) Absorption and (c) PL spectra of HDA-coated CdSe/CdS/ZnS QDs from toluene and [CdSe/CdS/ZnS]/POEGco-PDMA QDs in water.
DZ diffusion constants for the aggregates are smaller in the presence of increasing concentrations of APP. Estimating the solution viscosity as a weighted linear average of that of water and APP leads to the suggestion of small increases in Rh values for the aggregates in the presence of APP (see Table S1 in the Supporting Information). We are not convinced that these differences are meaningful. The main conclusion to be drawn from these experiments is that APP is able to penetrate into the clusters and passivate surface traps on the CdSe/ZnS QDs. Papadimitrakopoulos and co-workers47 reported that the treatment of TOPO-coated CdSe QDs in APP/water (10:1, v/v) mixture at 80 C in the presence of oxygen led to a slow chemical etching process of the CdSe core. This chemical etching over 60-90 h caused a significant blue shift for both the absorption and the PL spectra of the QDs. In contrast, we did not observe any spectral shift in our system of [CdSe/ZnS]/POEG-co-PDMA APP, which may be attributed to the protection of the CdSe core by the ZnS shell, or POEG-co-PDMA, or both. Ligand Exchange [CdSe/CdS/ZnS]/HDA with POEGco-PDMA. Ligand exchange of [CdSe/CdS/ZnS]/HDA core/ shell/shell QDs with POEG-co-PDMA was carried out in a 1:1 by
DOI: 10.1021/la900614e
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volume mixture of toluene/THF as described above for CdSe/ ZnS/TOPO QDs. After 4 precipitation/redispersion cycles, followed by drying under a vacuum, the QDs were easily dispersed in water. Figure 7 shows a TEM image of a [CdSe/CdS/ZnS]/ POEG-co-PDMA obtained from a solution in water. The absence of individual particles in this image suggests that aggregates are present in water, as inferred for [CdSe/ZnS]/POEG-co-PDMA, but we had too little QD sample to carry out DLS experiments on this system. Thus we confine our comments to the spectroscopic behavior of this system in water. The overall features of the absorption and PL spectra of [CdSe/ CdS/ZnS]/POEG-co-PDMA in water (Figures 4b and 4c) are similar to those of [CdSe/CdS/ZnS]/PEG-b-PDMA. We note that the PL QY of the QDs coated with the statistical copolymer (27%) was higher than that of the same QDs coated with the block copolymer (16%). The addition of APP (0.5 mL, dissolved in 2.0 mL of water) to an aqueous dispersion of [CdSe/CdS/ZnS]/ POEG-co-PDMA (0.5 mL) also increased the PL intensity (see Figure S3 in the Supporting Information). Here the 45% increase was not as pronounced as the more than 2-fold increase in the case of [CdSe/CdS/ZnS]/PEG-b-PDMA, but the QY prior to the addition of APP was significantly larger.
Summary
HDA-coated CdSe/CdS/ZnS core/shell/shell QDs and TOPOcoated CdSe/ZnS core/shell QDs could be dispersed into water following ligand exchange with a PEG-b-PDMA block copolymer or a statistical POEG-co-PDMA copolymer. These polymercoated QDs showed excellent colloidal stability in water. Previous experiments26 with PEG-b-PDMA block-copolymer-stabilized CdSe QDs indicated that the block copolymer stabilized individual QDs in aqueous solution. TEM images of the blockcopolymer-stabilized core-shell QDs suggest that a similar situation was obtained here. A greater abundance of sample permitted detailed dynamic light scattering studies of the interaction of the POEG-co-PDMA copolymer with the CdSe/ZnS core-shell QDs. THF and methanol solutions consisted largely of individual polymer-coated QDs (Rh = 11 nm) accompanied by a small amount of larger aggregates. In contrast, in water, the [CdSe/ZnS]/POEG-co-PDMA system consisted of a narrow distribution of aggregates with Rh = 54 nm. Addition of substantial amounts of APP to these solutions did not disrupt the aggregates, suggesting that they were held in place by multiple bridging interactions in which polymer chains interacted with the surfaces of more than one QD. These polymer-coated QDs also showed much higher quantum yields and long-term optical stability than samples of PEG-bPDMA block-copolymer-stabilized CdSe QDs in water. The enhanced QY and chemical stability of the QDs is, of course, a
consequence of surface passivation of the CdSe core by the ZnS shell. The double shell of CdS/ZnS imparts higher protection for the CdSe core than a single ZnS shell. Nevertheless, the photoluminescence QY of the [CdSe/CdS/ ZnS]/polymer QDs decreased upon transfer from an organic medium to water. The decrease in the PL intensity of both CdSe/CdS/ZnS core/shell/shell and CdSe/ZnS core/shell QDs after ligand exchange followed by dispersion into water suggests that the shell is relatively thin and that the encapsulation is not perfect. Surface traps may still exist on surfaces of these QD samples. Much of this loss in brightness could be restored by the addition of an excess of a water-soluble primary amine such as 3-amino-propanol (APP) to the solution. Similar photoluminescence enhancement was observed in [CdSe/ZnS]/ POEG-coPDMA in water. This chemical-activation strategy of adding primary amines as PL activators to polymer-stabilized QDs did not lead to any spectral shift of either the absorption or emission of the QDs in water. Although the underlying mechanism of intensity enhancement is not known, we speculate that these amine ligands may donate electrons to the surface electron traps, rendering them incapable of accepting electrons from the dot, hence reducing charge recombination through the traps.45,50 Other organic substances in water also had an influence on the brightness of the core-shell QD emission. Pyridine provided weak enhancement, whereas 3-aminomethylpyridine was as effective as APP. Imidazole was a weak quencher, whereas 2-mercaptoethaol led to a significant decrease in emission intensity. Acknowledgment. The authors thank NSERC Canada for its financial support and Dr. M. Hines at Evident Technologies for providing the CdSe/CdS/ZnS and CdSe/ZnS QD samples. Supporting Information Available: We provide UV-vis and PL spectra of CdSe/CdS/ZnS/PEG-b-PDMA in the presence of different concentrations of NaCl; PL spectra of CdSe/CdS/ZnS/PEG-b-PDMA after photoirradiation in water; UV-vis and PL spectra of CdSe/CdS/ZnS/POEGco-PDMA in water in the presence of APP; of CdSe/ZnS/ POEG-co-PDMA in water in the presence of various concentration of APP; a 1H NMR spectrum of POEG-coPDMA; autocorrelation decay traces and CONTIN plots for CdSe/ZnS/POEG-co-PDMA in water in the presence of various concentrations of APP; autocorrelation decay plots of CdSe/ZnS/POEG-co-PDMA in THF, methanol and water; a table of estimated Rh values. This material is available free of charge via the Internet at http://pubs.acs.org.
(50) Chen, Y.; Vela, J.; Htoon, H.; Casson, J. L.; Werder, D. J.; Bussian, D. A.; Klimov, V. I.; Hollingsworth, J. A. J. Am. Chem. Soc. 2008, 130, 50265027.