The surface science of nanocrystals

Murray, C. B., Kagan, C. R. & Bawendi, M. G. Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu. Rev. Mater. Sci. 30, 545–610 (2000).

Ozbay, E. Plasmonics: Merging photonics and electronics at nanoscale dimensions. Science 311, 189–193 (2006).

Bell, A. T. The impact of nanoscience on heterogeneous catalysis. Science 299, 1688–1691 (2003).

Giessibl, F. J. Atomic resolution of the silicon (111)-(7×7) surface by atomic force microscopy. Science 267, 68–71 (1995).

Chadi, D. J. Atomic and electronic structures of reconstructed Si(100) surfaces. Phys. Rev. Lett. 43, 43–47 (1979).

Laibinis, P. E. et al. Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, copper, silver, and gold. J. Am. Chem. Soc. 113, 7152–7167 (1991).

Yin, Y. & Alivisatos, A. P. Colloidal nanocrystal synthesis and the organic–inorganic interface. Nature 437, 664–670 (2005).

Kovalenko, M. V., Scheele, M. & Talapin, D. V. Colloidal nanocrystals with molecular metal chalcogenide surface ligands. Science 324, 1417–1420 (2009).

Nag, A. et al. Metal-free inorganic ligands for colloidal nanocrystals: S2−, HS−, Se2−, HSe−, Te2−, HTe−, TeS32−, OH−, and NH2− as surface ligands. J. Am. Chem. Soc. 133, 10612–10620 (2011).

Llordes, A., Garcia, G., Gazquez, J. & Milliron, D. J. Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites. Nature 500, 323–326 (2013).

Pellegrino, T. et al. Hydrophobic nanocrystals coated with an amphiphilic polymer shell: a general route to water soluble nanocrystals. Nano Lett. 4, 703–707 (2004).

Peng, X. et al. Shape control of CdSe nanocrystals. Nature 404, 59–61 (2000).

Ithurria, S. et al. Colloidal nanoplatelets with two-dimensional electronic structure. Nature Mater. 10, 936–941 (2011).

Nuzzo, R. G., Zegarski, B. R. & Dubois, L. H. Fundamental studies of the chemisorption of organosulfur compounds on gold(111). Implications for molecular self-assembly on gold surfaces. J. Am. Chem. Soc. 109, 733–740 (1987).

Dubois, L. H., Zegarski, B. R. & Nuzzo, R. G. Molecular ordering of organosulfur compounds on Au(111) and Au(100): adsorption from solution and in ultrahigh vacuum. J. Chem. Phys. 98, 678–688 (1993).

Dubois, L. H. & Nuzzo, R. G. Synthesis, structure, and properties of model organic surfaces. Annu. Rev. Phys. Chem. 43, 437–463 (1992).

Hakkinen, H. The gold–sulfur interface at the nanoscale. Nature Chem. 4, 443–455 (2012).

Hostetler, M. J., Stokes, J. J. & Murray, R. W. Infrared spectroscopy of three-dimensional self-assembled monolayers: n-alkanethiolate monolayers on gold cluster compounds. Langmuir 12, 3604–3612 (1996).

Badia, A., Cuccia, L., Demers, L., Morin, F. & Lennox, R. B. Structure and dynamics in alkanethiolate monolayers self-assembled on gold nanoparticles: a DSC, FT-IR, and deuterium NMR study. J. Am. Chem. Soc. 119, 2682–2692 (1997).

Frederick, M. T., Achtyl, J. L., Knowles, K. E., Weiss, E. A. & Geiger, F. M. Surface-amplified ligand disorder in CdSe quantum dots determined by electron and coherent vibrational spectroscopies. J. Am. Chem. Soc. 133, 7476–7481 (2011).

Morris-Cohen, A. J., Malicki, M., Peterson, M. D., Slavin, J. W. J. & Weiss, E. A. Chemical, structural, and quantitative analysis of the ligand shells of colloidal quantum dots. Chem. Mater. 25, 1155–1165 (2013).

Protesescu, L. et al. Atomistic description of thiostannate-capped CdSe nanocrystals: retention of four-coordinate SnS4 motif and preservation of Cd-rich stoichiometry. J. Am. Chem. Soc. 137, 1862–1874 (2015).

Green, M. L. H. A new approach to the formal classification of covalent compounds of the elements. J. Organomet. Chem. 500, 127–148 (1995).

Anderson, N. C., Hendricks, M. P., Choi, J. J. & Owen, J. S. Ligand exchange and the stoichiometry of metal chalcogenide nanocrystals: spectroscopic observation of facile metal–carboxylate displacement and binding. J. Am. Chem. Soc. 135, 18536–18548 (2013).

Owen, J. The coordination chemistry of nanocrystal surfaces. Science 347, 615–616 (2015).

Green, M. L. H. & Parkin, G. Application of the covalent bond classification method for the teaching of inorganic chemistry. J. Chem. Educ. 91, 807–816 (2014).

De Roo, J. et al. Carboxylic-acid-passivated metal oxide nanocrystals: ligand exchange characteristics of a new binding motif. Angew. Chem. Int. Ed. 54, 6488–6491 (2015).

Moreels, I. et al. Composition and size-dependent extinction coefficient of colloidal PbSe quantum dots. Chem. Mater. 19, 6101–6106 (2007).

Luther, J. M. & Pietryga, J. M. Stoichiometry control in quantum dots: a viable analog to impurity doping of bulk materials. ACS Nano 7, 1845–1849 (2013).

Israelachvili, J. N. Intermolecular and Surface Forces (Elsevier, 2011).

Zherebetskyy, D. et al. Hydroxylation of the surface of PbS nanocrystals passivated with oleic acid. Science 344, 1380–1384 (2014).

Fritzinger, B. et al. In situ observation of rapid ligand exchange in colloidal nanocrystal suspensions using transfer NOE nuclear magnetic resonance spectroscopy. J. Am. Chem. Soc. 131, 3024–3032 (2009).

Fritzinger, B., Capek, R. K., Lambert, K., Martins, J. C. & Hens, Z. Utilizing self-exchange to address the binding of carboxylic acid ligands to CdSe quantum dots. J. Am. Chem. Soc. 132, 10195–10201 (2010).

Gomes, R. et al. Binding of phosphonic acids to CdSe quantum dots: a solution NMR study. J. Phys. Chem. Lett. 2, 145–152 (2011).

Lingley, Z., Lu, S. & Madhukar, A. A high quantum efficiency preserving approach to ligand exchange on lead sulfide quantum dots and interdot resonant energy transfer. Nano Lett. 11, 2887–2891 (2011).

Hostetler, M. J., Templeton, A. C. & Murray, R. W. Dynamics of place-exchange reactions on monolayer-protected gold cluster molecules. Langmuir 15, 3782–3789 (1999).

Owen, J. S., Park, J., Trudeau, P.-E. & Alivisatos, A. P. Reaction chemistry and ligand exchange at cadmium–selenide nanocrystal surfaces. J. Am. Chem. Soc. 130, 12279–12281 (2008).

Murray, C. B., Norris, D. J. & Bawendi, M. G. Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites. J. Am. Chem. Soc. 115, 8706–8715 (1993).

Gur, I., Fromer, N. A., Geier, M. L. & Alivisatos, A. P. Air-stable all-inorganic nanocrystal solar cells processed from solution. Science 310, 462–465 (2005).

Fedin, I. & Talapin, D. V. Probing the surface of colloidal nanomaterials with potentiometry in situ. J. Am. Chem. Soc. 136, 11228–11231 (2014).

Rosen, E. L. et al. Exceptionally mild reactive stripping of native ligands from nanocrystal surfaces by using Meerwein's salt. Angew. Chem. Int. Ed. 51, 684–689 (2012).

Pearson, R. G. Absolute electronegativity and hardness: application to inorganic chemistry. Inorg. Chem. 27, 734–740 (1988).

Xu, C. et al. Dopamine as a robust anchor to immobilize functional molecules on the iron oxide shell of magnetic nanoparticles. J. Am. Chem. Soc. 126, 9938–9939 (2004).

Uyeda, H. T., Medintz, I. L., Jaiswal, J. K., Simon, S. M. & Mattoussi, H. Synthesis of compact multidentate ligands to prepare stable hydrophilic quantum dot fluorophores. J. Am. Chem. Soc. 127, 3870–3878 (2005).

Webber, D. H. & Brutchey, R. L. Ligand exchange on colloidal CdSe nanocrystals using thermally labile tert-butylthiol for improved photocurrent in nanocrystal films. J. Am. Chem. Soc. 134, 1085–1092 (2011).

Munro, A. M., Jen- La Plante, I., Ng, M. S. & Ginger, D. S. Quantitative study of the effects of surface ligand concentration on CdSe nanocrystal photoluminescence. J. Phys. Chem. C 111, 6220–6227 (2007).

Brus, L. Electronic wave functions in semiconductor clusters: experiment and theory. J. Phys. Chem. 90, 2555–2560 (1986).

Ip, A. H. et al. Hybrid passivated colloidal quantum dot solids. Nature Nanotech. 7, 577–582 (2012).

Aldana, J., Wang, Y. A. & Peng, X. Photochemical instability of CdSe nanocrystals coated by hydrophilic thiols. J. Am. Chem. Soc. 123, 8844–8850 (2001).

Brown, P. R. et al. Energy level modification in lead sulfide quantum dot thin films through ligand exchange. ACS Nano 8, 5863–5872 (2014).

Chuang, C.-H. M., Brown, P. R., Bulović, V. & Bawendi, M. G. Improved performance and stability in quantum dot solar cells through band alignment engineering. Nature Mater. 13, 796–801 (2014).

Ning, Z. et al. Air-stable n-type colloidal quantum dot solids. Nature Mater. 13, 822–828 (2014).

Boyer, J. L., Rochford, J., Tsai, M.-K., Muckerman, J. T. & Fujita, E. Ruthenium complexes with non-innocent ligands: electron distribution and implications for catalysis. Coord. Chem. Rev. 254, 309–330 (2010).

Frederick, M. T. & Weiss, E. A. Relaxation of exciton confinement in CdSe quantum dots by modification with a conjugated dithiocarbamate ligand. ACS Nano 4, 3195–3200 (2010).

Malinsky, M. D., Kelly, K. L., Schatz, G. C. & Van Duyne, R. P. Chain length dependence and sensing capabilities of the localized surface plasmon resonance of silver nanoparticles chemically modified with alkanethiol self-assembled monolayers. J. Am. Chem. Soc. 123, 1471–1482 (2001).

Kwon, S. G. et al. Capping ligands as selectivity switchers in hydrogenation reactions. Nano Lett. 12, 5382–5388 (2012).

Duan, H. et al. Reexamining the effects of particle size and surface chemistry on the magnetic properties of iron oxide nanocrystals: new insights into spin disorder and proton relaxivity. J. Phys. Chem. C 112, 8127–8131 (2008).

Shevchenko, E. V., Talapin, D. V., Kotov, N. A., O'Brien, S. & Murray, C. B. Structural diversity in binary nanoparticle superlattices. Nature 439, 55–59 (2006).

Lee, J., Sundar, V. C., Heine, J. R., Bawendi, M. G. & Jensen, K. F. Full color emission from II–VI semiconductor quantum dot–polymer composites. Adv. Mater. 12, 1102–1105 (2000).

Howes, P. D., Chandrawati, R. & Stevens, M. M. Colloidal nanoparticles as advanced biological sensors. Science 346, 1247390 (2014).

Talapin, D. V., Lee, J.-S., Kovalenko, M. V. & Shevchenko, E. V. Prospects of colloidal nanocrystals for electronic and optoelectronic applications. Chem. Rev. 110, 389–458 (2010).

Bruchez, M., Moronne, M., Gin, P., Weiss, S. & Alivisatos, A. P. Semiconductor nanocrystals as fluorescent biological labels. Science 281, 2013–2016 (1998).

Chan, W. C. W. & Nie, S. Quantum dot bioconjugates for ultrasensitive nonisotopic detection. Science 281, 2016–2018 (1998).

Dubertret, B. et al. In vivo imaging of quantum dots encapsulated in phospholipid micelles. Science 298, 1759–1762 (2002).

Osaki, F., Kanamori, T., Sando, S., Sera, T. & Aoyama, Y. A quantum dot conjugated sugar ball and its cellular uptake. On the size effects of endocytosis in the subviral region. J. Am. Chem. Soc. 126, 6520–6521 (2004).

Gao, X., Cui, Y., Levenson, R. M., Chung, L. W. K. & Nie, S. In vivo cancer targeting and imaging with semiconductor quantum dots. Nature Biotechnol. 22, 969–976 (2004).

Choi, S. H. et al. Renal clearance of quantum dots. Nature Biotechnol. 25, 1165–1170 (2007).

Mitchell, G. P., Mirkin, C. A. & Letsinger, R. L. Programmed assembly of DNA functionalized quantum dots. J. Am. Chem. Soc. 121, 8122–8123 (1999).

Mattoussi, H. et al. Self-assembly of CdSe−ZnS quantum dot bioconjugates using an engineered recombinant protein. J. Am. Chem. Soc. 122, 12142–12150 (2000).

Lee, J.-H. et al. Artificially engineered magnetic nanoparticles for ultra-sensitive molecular imaging. Nature Med. 13, 95–99 (2007).

Susumu, K. et al. Enhancing the stability and biological functionalities of quantum dots via compact multifunctional ligands. J. Am. Chem. Soc. 129, 13987–13996 (2007).

Liu, W. et al. Compact biocompatible quantum dots functionalized for cellular imaging. J. Am. Chem. Soc. 130, 1274–1284 (2008).

Stewart, M. H. et al. Multidentate poly(ethylene glycol) ligands provide colloidal stability to semiconductor and metallic nanocrystals in extreme conditions. J. Am. Chem. Soc. 132, 9804–9813 (2010).

Zhan, N., Palui, G., Safi, M., Ji, X. & Mattoussi, H. Multidentate zwitterionic ligands provide compact and highly biocompatible quantum dots. J. Am. Chem. Soc. 135, 13786–13795 (2013).

Kim, S. & Bawendi, M. G. Oligomeric ligands for luminescent and stable nanocrystal quantum dots. J. Am. Chem. Soc. 125, 14652–14653 (2003).

Na, H. B. et al. Multidentate catechol-based polyethylene glycol oligomers provide enhanced stability and biocompatibility to iron oxide nanoparticles. ACS Nano 6, 389–399 (2011).

Medintz, I. L. et al. Self-assembled nanoscale biosensors based on quantum dot FRET donors. Nature Mater. 2, 630–638 (2003).

Medintz, I. L., Uyeda, H. T., Goldman, E. R. & Mattoussi, H. Quantum dot bioconjugates for imaging, labelling and sensing. Nature Mater. 4, 435–446 (2005).

Pinaud, F., King, D., Moore, H.-P. & Weiss, S. Bioactivation and cell targeting of semiconductor CdSe/ZnS nanocrystals with phytochelatin-related peptides. J. Am. Chem. Soc. 126, 6115–6123 (2004).

Liu, W. et al. Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand. J. Am. Chem. Soc. 132, 472–483 (2010).

Ellis, R. J. Macromolecular crowding: obvious but underappreciated. Trends Biochem. Sci. 26, 597–604 (2001).

Harris, J. M. & Chess, R. B. Effect of pegylation on pharmaceuticals. Nature Rev. Drug Discov. 2, 214–221 (2003).

Israelachvili, J. The different faces of poly(ethylene glycol). Proc. Natl Acad. Sci. USA 94, 8378–8379 (1997).

Walkey, C. D., Olsen, J. B., Guo, H., Emili, A. & Chan, W. C. W. Nanoparticle size and surface chemistry determine serum protein adsorption and macrophage uptake. J. Am. Chem. Soc. 134, 2139–2147 (2011).

Moyano, D. F. et al. Fabrication of corona-free nanoparticles with tunable hydrophobicity. ACS Nano 8, 6748–6755 (2014).

Yildiz, I. et al. Hydrophilic CdSe−ZnS core−shell quantum dots with reactive functional groups on their surface. Langmuir 26, 11503–11511 (2010).

Ling, D. et al. Multifunctional tumor pH-sensitive self-assembled nanoparticles for bimodal imaging and treatment of resistant heterogeneous tumors. J. Am. Chem. Soc. 136, 5647–5655 (2014).

Giovanelli, E. et al. Highly enhanced affinity of multidentate versus bidentate zwitterionic ligands for long-term quantum dot bioimaging. Langmuir 28, 15177–15184 (2012).

Zhang, P. et al. Click-functionalized compact quantum dots protected by multidentate-imidazole ligands: conjugation-ready nanotags for living-virus labeling and imaging. J. Am. Chem. Soc. 134, 8388–8391 (2012).

Blanco-Canosa, J. B., Medintz, I. L., Farrell, D., Mattoussi, H. & Dawson, P. E. Rapid covalent ligation of fluorescent peptides to water solubilized quantum dots. J. Am. Chem. Soc. 132, 10027–10033 (2010).

Han, H.-S. et al. Development of a bioorthogonal and highly efficient conjugation method for quantum dots using tetrazine−norbornene cycloaddition. J. Am. Chem. Soc. 132, 7838–7839 (2010).

Mura, S., Nicolas, J. & Couvreur, P. Stimuli-responsive nanocarriers for drug delivery. Nature Mater. 12, 991–1003 (2013).

Ling, D., Hackett, M. J. & Hyeon, T. Surface ligands in synthesis, modification, assembly and biomedical applications of nanoparticles. Nano Today 9, 457–477 (2014).

Talapin, D. V. & Steckel, J. Quantum dot light-emitting devices. MRS Bull. 38, 685–695 (2013).

Talapin, D. V. & Murray, C. B. PbSe nanocrystal solids for n- and p-channel thin film field-effect transistors. Science 310, 86–89 (2005).

Kovalenko, M. V., Bodnarchuk, M. I., Zaumseil, J., Lee, J.-S. & Talapin, D. V. Expanding the chemical versatility of colloidal nanocrystals capped with molecular metal chalcogenide ligands. J. Am. Chem. Soc. 132, 10085–10092 (2010).

Luther, J. M. et al. Structural, optical, and electrical properties of self-assembled films of PbSe nanocrystals treated with 1,2-ethanedithiol. ACS Nano 2, 271–280 (2008).

Dolzhnikov, D. S. et al. Composition-matched molecular 'solders' for semiconductors. Science 347, 425–428 (2015).

Dirin, D. N. et al. Lead halide perovskites and other metal halide complexes as inorganic capping ligands for colloidal nanocrystals. J. Am. Chem. Soc. 136, 6550–6553 (2014).

Zhang, H., Jang, J., Liu, W. & Talapin, D. V. Colloidal nanocrystals with inorganic halide, pseudohalide, and halometallate ligands. ACS Nano 8, 7359–7369 (2014).

Fafarman, A. T. et al. Thiocyanate-capped nanocrystal colloids: vibrational reporter of surface chemistry and solution-based route to enhanced coupling in nanocrystal solids. J. Am. Chem. Soc. 133, 15753–15761 (2011).

Oh, S. J. et al. Engineering charge injection and charge transport for high performance PbSe nanocrystal thin film devices and circuits. Nano Lett. 14, 6210–6216 (2014).

Choi, J.-H. et al. Bandlike transport in strongly coupled and doped quantum dot solids: a route to high-performance thin-film electronics. Nano Lett. 12, 2631–2638 (2012).

Lee, J.-S., Kovalenko, M. V., Huang, J., Chung, D. S. & Talapin, D. V. Band-like transport, high electron mobility and high photoconductivity in all-inorganic nanocrystal arrays. Nature Nanotech. 6, 348–352 (2011).

Kim, D. K., Lai, Y., Diroll, B. T., Murray, C. B. & Kagan, C. R. Flexible and low-voltage integrated circuits constructed from high-performance nanocrystal transistors. Nature Commun. 3, 1216 (2012).

Shabaev, A., Efros, A. L. & Efros, A. L. Dark and photo-conductivity in ordered array of nanocrystals. Nano Lett. 13, 5454–5461 (2013).

Crisp, R. W., Schrauben, J. N., Beard, M. C., Luther, J. M. & Johnson, J. C. Coherent exciton delocalization in strongly coupled quantum dot arrays. Nano Lett. 13, 4862–4869 (2013).

Jang, J., Liu, W., Son, J. S. & Talapin, D. V. Temperature-dependent Hall and field-effect mobility in strongly coupled all-inorganic nanocrystal arrays. Nano Lett. 14, 653–662 (2014).

Jeong, K. S. et al. Enhanced mobility-lifetime products in PbS colloidal quantum dot photovoltaics. ACS Nano 6, 89–99 (2012).

Zhitomirsky, D. et al. Engineering colloidal quantum dot solids within and beyond the mobility-invariant regime. Nature Commun. 5, 1–7 (2014).

Tang, J. et al. Colloidal-quantum-dot photovoltaics using atomic-ligand passivation. Nature Mater. 10, 765–771 (2011).

Kovalenko, M. V., Schaller, R. D., Jarzab, D., Loi, M. A. & Talapin, D. V. Inorganically functionalized PbS–CdS colloidal nanocrystals: integration into amorphous chalcogenide glass and luminescent properties. J. Am. Chem. Soc. 134, 2457–2460 (2012).

Panthani, M. G. et al. Synthesis of CuInS2, CuInSe2, and Cu(InxGa1-x)Se2 (CIGS) nanocrystal inks for printable photovoltaics. J. Am. Chem. Soc. 130, 16770–16777 (2008).

Panthani, M. G. et al. High efficiency solution processed sintered CdTe nanocrystal solar cells: the role of interfaces. Nano Lett. 14, 670–675 (2014).

Jiang, C., Lee, J.-S. & Talapin, D. V. Soluble precursors for CuInSe2, CuIn1–xGaxSe2, and Cu2ZnSn(S,Se)4 based on colloidal nanocrystals and molecular metal chalcogenide surface ligands. J. Am. Chem. Soc. 134, 5010–5013 (2012).

Son, J. S. et al. All-inorganic nanocrystals as a glue for BiSbTe grains: design of interfaces in mesostructured thermoelectric materials. Angew. Chem. Int. Ed. 53, 7466–7470 (2014).

Boles, M. A. & Talapin, D. V. Connecting the dots. Science 344, 1340–1341 (2014).

Protesescu, L. et al. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett. 15, 3692–3696 (2015).

Mattoussi, H., Cumming, A. W., Murray, C. B., Bawendi, M. G. & Ober, R. Properties of CdSe nanocrystal dispersions in the dilute regime: structure and interparticle interactions. Phys. Rev. B 58, 7850–7863 (1998).

Saunders, A. E. & Korgel, B. A. Second virial coefficient measurements of dilute gold nanocrystal dispersions using small-angle X-ray scattering. J. Phys. Chem. B 108, 16732–16738 (2004).

Schapotschnikow, P., Pool, R. & Vlugt, T. J. H. Molecular simulations of interacting nanocrystals. Nano Lett. 8, 2930–2934 (2008).

Hens, Z. & Martins, J. C. A solution NMR toolbox for characterizing the surface chemistry of colloidal nanocrystals. Chem. Mater. 25, 1211–1221 (2013).

Schapotschnikow, P., Hommersom, B. & Vlugt, T. J. H. Adsorption and binding of ligands to CdSe nanocrystals. J. Phys. Chem. C 113, 12690–12698 (2009).

Panthani, M. G. et al. Graphene-supported high-resolution TEM and STEM imaging of silicon nanocrystals and their capping ligands. J. Phys. Chem. C 116, 22463–22468 (2012).