Semiconductor nanocrystals: structure, properties, and band gap engineering.

Semiconductor nanocrystals are tiny light-emitting particles on the nanometer scale. Researchers have studied these particles intensely and have developed them for broad applications in solar energy conversion, optoelectronic devices, molecular and cellular imaging, and ultrasensitive detection. A major feature of semiconductor nanocrystals is the quantum confinement effect, which leads to spatial enclosure of the electronic charge carriers within the nanocrystal. Because of this effect, researchers can use the size and shape of these "artificial atoms" to widely and precisely tune the energy of discrete electronic energy states and optical transitions. As a result, researchers can tune the light emission from these particles throughout the ultraviolet, visible, near-infrared, and mid-infrared spectral ranges. These particles also span the transition between small molecules and bulk crystals, instilling novel optical properties such as carrier multiplication, single-particle blinking, and spectral diffusion. In addition, semiconductor nanocrystals provide a versatile building block for developing complex nanostructures such as superlattices and multimodal agents for molecular imaging and targeted therapy. In this Account, we discuss recent advances in the understanding of the atomic structure and optical properties of semiconductor nanocrystals. We also discuss new strategies for band gap and electronic wave function engineering to control the location of charge carriers. New methodologies such as alloying, doping, strain-tuning, and band-edge warping will likely play key roles in the further development of these particles for optoelectronic and biomedical applications.

[1]  Benoit Dubertret,et al.  Quasi 2D colloidal CdSe platelets with thicknesses controlled at the atomic level. , 2008, Journal of the American Chemical Society.

[2]  Lin-Wang Wang,et al.  Synthesis of cadmium telluride quantum wires and the similarity of their effective band gaps to those of equidiameter cadmium telluride quantum dots. , 2008, Journal of the American Chemical Society.

[3]  J. Vela,et al.  "Giant" multishell CdSe nanocrystal quantum dots with suppressed blinking. , 2008, Journal of the American Chemical Society.

[4]  D. W. Hall,et al.  Quantum confinement effects of semiconducting microcrystallites in glass , 1987 .

[5]  U. Banin,et al.  Determination of band offsets in heterostructured colloidal nanorods using scanning tunneling spectroscopy. , 2008, Nano letters.

[6]  A. Mohs,et al.  Tuning the optical and electronic properties of colloidal nanocrystals by lattice strain. , 2009, Nature nanotechnology.

[7]  M. Nirmal,et al.  Fluorescence intermittency in single cadmium selenide nanocrystals , 1996, Nature.

[8]  S. Dimitrov,et al.  Ultrafast Electron Transfer Dynamics in CdSe/CdTe Donor−Acceptor Nanorods , 2008 .

[9]  P. Mulvaney,et al.  Optical properties of single semiconductor nanocrystals. , 2006, Physical chemistry chemical physics : PCCP.

[10]  P. Guyot-Sionnest,et al.  Mn2+ as a radial pressure gauge in colloidal core/shell nanocrystals. , 2007, Physical review letters.

[11]  A. Alivisatos Perspectives on the Physical Chemistry of Semiconductor Nanocrystals , 1996 .

[12]  Klimov,et al.  Quantization of multiparticle auger rates in semiconductor quantum dots , 2000, Science.

[13]  S. Rosenthal,et al.  Ultrafast Carrier Dynamics in CdSe Nanocrystals Determined by Femtosecond Fluorescence Upconversion Spectroscopy , 2001 .

[14]  Louis E. Brus,et al.  The Quantum Mechanics of Larger Semiconductor Clusters ("Quantum Dots") , 1990 .

[15]  Shuming Nie,et al.  Bioconjugated quantum dots for in vivo molecular and cellular imaging. , 2008, Advanced drug delivery reviews.

[16]  Liberato Manna,et al.  Controlled growth of tetrapod-branched inorganic nanocrystals , 2003, Nature materials.

[17]  V. Klimov Spectral and dynamical properties of multiexcitons in semiconductor nanocrystals. , 2007, Annual review of physical chemistry.

[18]  M Celebrano,et al.  Imaging a single quantum dot when it is dark. , 2009, Nano letters.

[19]  P. Jain,et al.  (CdSe)ZnS Core−Shell Quantum Dots: Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites , 2009 .

[20]  Watt W Webb,et al.  Blinking and nonradiant dark fraction of water-soluble quantum dots in aqueous solution. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[21]  Moungi G. Bawendi,et al.  Spectroscopy of Single CdSe Nanocrystallites , 1999 .

[22]  M. Yin,et al.  Tunable magnetic exchange interactions in manganese-doped inverted core-shell ZnSe-CdSe nanocrystals. , 2008, Nature materials.

[23]  Christopher B. Murray,et al.  Synthesis and characterization of nearly monodisperse CdE (E = S, Se, Te) semiconductor nanocrystallites , 2005 .

[24]  Simone Pokrant,et al.  Tight-binding studies of surface effects on electronic structure of CdSe nanocrystals: the role of organic ligands, surface reconstruction, and inorganic capping shells , 1999 .

[25]  Uri Banin,et al.  Fluorescence quantum yield of CdSe/ZnS nanocrystals investigated by correlated atomic-force and single-particle fluorescence microscopy , 2002 .

[26]  John Silcox,et al.  Non-blinking semiconductor nanocrystals , 2009, Nature.

[27]  James McBride,et al.  Structural basis for near unity quantum yield core/shell nanostructures. , 2006, Nano letters.

[28]  S. Tolbert,et al.  High-pressure structural transformations in semiconductor nanocrystals. , 1995, Annual review of physical chemistry.

[29]  A. P. Alivisatos,et al.  Shape control and applications of nanocrystals , 2003, Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[30]  M. Bawendi,et al.  Room-temperature ordered photon emission from multiexciton states in single CdSe core-shell nanocrystals. , 2005, Physical review letters.

[31]  B. Dubertret,et al.  Towards non-blinking colloidal quantum dots. , 2008, Nature materials.

[32]  A. Zunger,et al.  Carrier multiplication in semiconductor nanocrystals: theoretical screening of candidate materials based on band-structure effects. , 2008, Nano letters.

[33]  Louis E. Brus,et al.  Electron-electron and electron-hole interactions in small semiconductor crystallites : The size dependence of the lowest excited electronic state , 1984 .

[34]  Shuming Nie,et al.  Oxidative quenching and degradation of polymer-encapsulated quantum dots: new insights into the long-term fate and toxicity of nanocrystals in vivo. , 2008, Journal of the American Chemical Society.

[35]  G. Scholes,et al.  Nanorod heterostructures showing photoinduced charge separation. , 2007, Small.

[36]  Wolfgang Knoll,et al.  Alloyed Zn(x)Cd(1-x)S nanocrystals with highly narrow luminescence spectral width. , 2003, Journal of the American Chemical Society.

[37]  Shuming Nie,et al.  Alloyed semiconductor quantum dots: tuning the optical properties without changing the particle size. , 2003, Journal of the American Chemical Society.

[38]  M. Bawendi,et al.  Type-II quantum dots: CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures. , 2003, Journal of the American Chemical Society.

[39]  Xiaogang Peng Mechanisms for the Shape‐Control and Shape‐Evolution of Colloidal Semiconductor Nanocrystals , 2003 .

[40]  Louis E. Brus,et al.  Luminescence Photophysics in Semiconductor Nanocrystals , 1999 .

[41]  Warnock,et al.  Quantum size effects in simple colored glass. , 1985, Physical review. B, Condensed matter.

[42]  Victor I. Klimov,et al.  Optical Nonlinearities and Ultrafast Carrier Dynamics in Semiconductor Nanocrystals , 2000 .

[43]  P. Guyot-Sionnest,et al.  Synthesis and Characterization of Strongly Luminescing ZnS-Capped CdSe Nanocrystals , 1996 .

[44]  Thomas A. Kennedy,et al.  Doping semiconductor nanocrystals , 2005, Nature.