Prospects of nanoscience with nanocrystals. - PDF Download Free (2024)

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Maksym V. Kovalenko,*,†,‡ Liberato Manna,§,^ Andreu Cabot, ,z Zeger Hens,#,4 Dmitri V. Talapin,2,3 Cherie R. Kagan,1,X Victor I. Klimov," Andrey L. Rogach,` Peter Reiss,¥ Delia J. Milliron,& Philippe Guyot-Sionnnest,2 Gerasimos Konstantatos,x Wolfgang J. Parak,0,f Taeghwan Hyeon,9,O Brian A. Korgel,&,b Christopher B. Murray,X and Wolfgang Heiss*,$,@,( †

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Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland, ‡Laboratory for Thin Films and Photovoltaics, EMPA Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland, §Nanochemistry Department, Italian Institute of Technology, Genoa, Italy, ^Kavli Institute of NanoScience, Delft University of Technology, 2628 CJ Delft, The Netherlands, Catalonia Energy Research Institute, Sant Adria del Besos 08930, Spain, zInstitució Catalana de Recerca i Estudis Avanc-ats, ICREA, Barcelona 08010, Spain, #Physics and Chemistry of Nanostructures and 4Center for Nano- and Biophotonics, Ghent University, Ghent, Belgium, 2Department of Chemistry and James Franck Institute, University of Chicago, Chicago, Illinois 60637, United States, 3Center for Nanoscale Materials, Argonne National Lab, Argonne, Illinois 60439, United States, 1Department of Electrical and Systems Engineering and XDepartment of Materials Science and Engineering and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States, "Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States, `Department of Physics and Materials Science and Centre for Functional Photonics, City University of Hong Kong, Kowloon, Hong Kong, ¥Laboratoire d'Electronique Moléculaire, Organique et Hybride, UMR 5819 SPrAM (CEA-INAC, CNRS, Univ. Grenoble Alpes, 38054 Grenoble, France, &McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712 United States, 0Philipps Universität Marburg, Marburg, Germany, fCIC Biomagune, San Sebastian, Spain, 9Center for Nanoparticle Research, Institute for Basic Science, Seoul 151-742, Korea, OSchool of Chemical and Biological Engineering, Seoul National University, Seoul 151-742, Korea, xICFO, The Institute of Photonic Sciences, 08860 Castelldefels, Spain, bTexas Materials Institute, Center for Nano- and Molecular Science and Technology, The University of Texas at Austin, Austin, Texas 78712, United States, $Institute of Semiconductor and Solid State Physics, Johannes Kepler University Linz, 4040 Linz, Austria, @Materials for Electronics and Energy Technology (i-MEET), Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany, and (Energie Campus Nürnberg, 90429 Nürnberg, Germany

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Prospects of Nanoscience with Nanocrystals

ABSTRACT Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications

ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and lightemitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In this Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.

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hermodynamically stable colloidal solutions of nanosized inorganic materials are well-described in colloidal chemistry textbooks as “sols” and have been known in a modern scientific context since the 19th century, with ruby-colored gold sols produced by Michael Faraday as one notable example.1 The birth of modern nanoscience with nanocrystals (NCs) is, however, attributed to a much later period: beginning in the early 1980s and extending to the present. Early photochemistry studies on tailored colloidal CdS and TiO2 arose from the oil crisis in the late 1970s, and semiconductor NCs with enhanced surface chemistry were considered highly KOVALENKO ET AL.

important for efficient harvesting of solar energy by means of photoelectrochemistry (A. Nozik, L. Brus, A. Henglein, and their co-workers).29 Semiconductor NCs were termed quantum dots (QDs) after the discovery and explanation of quantum size effects in the optical spectra of CuCl NCs embedded into glass and alkali-halide matrices (A. Ekimov, A. Onushchenko, A. Efros, T. Itoh, and co-workers)1012 and in aqueous solutions of colloidal CdS NCs (L. Brus and co-workers).68 Since the mid-1990s, colloidal QDs have become a masterpiece of NC research and one of the most accomplished building blocks of modern nanoscience due to the emergence of surfactant-assisted VOL. 9

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* Address correspondence to [emailprotected], [emailprotected]. Received for review October 31, 2014 Published online January 22, 2015 10.1021/nn506223h C 2015 American Chemical Society

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SYNTHESIS OF COLLOIDAL NANOCRYSTALS The accessible complexity of NCs is rapidly expanding, in terms of both compositional variety and shape engineering.1618 Much present-day research focuses on solving challenging problems in the synthesis of novel NCs and nanoparticles (NPs) such as the synthesis of highly covalent group IV elements (Si, Ge),1922 IIIV compounds (GaAs, InAs, InSb, etc.),2326 multicomponent chalcogenides, carbon nanostructures, or even organic compounds in the form of highly uniform NCs. Several recent examples are illustrated below. Continuing efforts are underway to engineer NC composition and morphology by KOVALENKO ET AL.

means of galvanic replacement,27,28 ion-exchange reactions,2932 or through the nanoscale Kirkendall effect.33,34 Even “classical” QD materials such as coreshell CdSe/ CdS NCs have recently been further perfected to yield above 90% luminescence quantum yields with narrowed emission lines and high photostability.35,36 Equally important are efforts toward the development and use of in situ characterization methods to obtain insights into the nucleation and growth of NCs or to monitor structural and compositional transformations in NCs directly in the electron microscope, as briefly reviewed below.

material but one that can emit light relatively efficiently as a nanostructure due to quantum confinement. Yet, Si has been one of the least studied colloidal NC materials because of the various challenges facing its synthesis, until recently. These challenges include the identification of suitable reaction pathways to generate Si atoms in a colloidal system, the tendency of Si to form stable amorphous structures and thus require relatively high temperatures for crystallization, its propensity to oxidize, and capping ligand chemistry that is significantly different from that of the well-studied metals and metal chalcogenides. One of the first relatively successful synthetic routes to Si NCs was developed by Brus and co-workers in the early 1990s, which employed an aerosol system that enabled high synthesis temperatures;much higher than those available in high boiling solvents.37 These NCs were made by pyrolysis of silane and were captured in stabilizing solvents like ethylene glycol. In this early work, the Si NC surfaces were intentionally oxidized to create an inorganic passivating shell. This approach worked well, but the tunability of the optical properties was relatively limited and the oxide shell created traps at the Si interface that limited the light emission from the NCs. To overcome these limitations, several different colloidal approaches have been explored, including metathesis reactions,38 silane reduction,39 and thermal decomposition of silanes in high-temperature supercritical fluids;40 however, none of these colloidal routes has provided a general, high-yield synthesis of Si NCs with widely tunable size and optical properties. Again, one of the challenges facing colloidal syntheses is the relatively low temperatures in these reaction systems. To date, two of the most successful methods for producing Si NCs with tunable size and optical properties are still aerosol methods. Swihart's group has developed a method using laser

The accessible complexity of NCs is rapidly expanding, in terms of both compositional variety and shape engineering. Colloidal Silicon Nanostructures. The field of nanomaterials chemistry aims to develop synthetic routes to produce macroscopic quantities of stable NCs with controlled and tunable size and shape. This is accomplished by employing reaction chemistry that yields the desired nanomaterial in the presence of capping ligands that bind to the NC surface and stabilize the material. This usually requires capping ligands with surface bonding that is at least partially reversible to enable NC growth up to a desired size. Considerable progress has been made recently in the development of chemical routes to silicon (Si) nanomaterials, including Si NCs, nanorods, and nanowires (Figure 1). Silicon is one of the most commercially important semiconductors and one of the most interesting to study at the nanoscale because it has an indirect band gap that makes it a poor light emitter as a bulk VOL. 9

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precision synthesis that provides narrow size distributions, highly uniform morphologies, well-controlled surface chemistry, and enhanced optical properties such as bright, spectrally tunable, and stable photoluminescence.1315 Since then, colloidal NCs are among the most modular and versatile nanoscale materials, due to both their unprecedented compositional and morphological tunability and their “free” (unsupported) colloidal state that allows their positioning onto various surfaces or integration into various matrices. These characteristics are hardly simultaneously achievable with any physical nanostructuring method, whether it is a top-down (e.g., electron beam lithography) or a bottom-up (e.g., molecular beam epitaxy) procedure. Beginning in the 2000s and until now, a multitude of metals, metal oxides, and semiconductors have been developed in the form of isotropic and anisotropic NCs. This Nano Focus article is structured into five main sections. First, we review the most recent trends in the synthesis of NCs, then we describe NC surface chemistry, selfassembled long-range-ordered NC superlattices, and novel applications of NCs, and finally, we discuss our vision for the future of this field.

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NANO FOCUS Figure 1. (A) Silicon nanocrystal superlattice (Inset: Fast Fourier transform of the image). Reprinted with permission from ref 19. Copyright 2013 Wiley Interscience. (B) Transmission electron microscopy (TEM) image of an octadecene-capped Si NC. Reprinted from ref 50. Copyright 2012 American Chemical Society. (C) Schematic of the ligand-assisted solutionliquidsolid (SLS) synthesis of Si nanorods. Reprinted from ref 51. Copyright 2009 American Chemical Society. (D) TEM image of a field of Si nanorods made with Sn seeds. (E) TEM image of two Si nanorods showing their crystal structure. (F) High-angle annular darkfield (HAADF) scanning transmission electron microscopy (STEM) image of a field of Si nanorods. (G) Room temperature optical properties of fluorescent Si nanorods. (DG) Reprinted from ref 20. Copyright 2013 American Chemical Society.

pyrolysis of silanes to produce large quantities of NCs, but in the >30 nm diameter size range. These are far too large to exhibit quantum confinement, but they can be captured and etched to smaller sizes and then passivated with alkenes by hydrosilylation.41,42 To obtain much smaller NCs in the aerosol phase, Kortshagen developed a nonthermal plasma approach to generate Si NCs in the quantum size regime that are captured in a solvent for subsequent hydrosilylation.43,44 Both methods work well but face limitations, especially in KOVALENKO ET AL.

method has thus far continued to elude the field. An approach that is close to a colloidal synthesis of Si NCs was developed by the Veinot group, which uses a high-temperature thermal decomposition of a SiO1.5 precursor, hydrogen silsequioxane (HSQ), to create Si NCs embedded in an oxide host.45 The NC diameter is widely tunable, from as small as ∼1.5 nm to more than 10 nm in diameter, depending on the temperature used to decompose HSQ. The Si NCs can then be liberated

producing NCs in the smaller range of sizes (∼2 nm in diameter, for instance). For example, high photoluminescence quantum yields of up to 60% can be achieved using plasma-based synthesis but only for NCs in the larger size range (above 4 nm in diameter), and the photoluminescence quantum yield drops significantly for smaller sizes. Ultimately, a direct arrested precipitation of Si NCs in a solventbased medium is desired to produce a wider range of sizes with wellpassivated NC surfaces, but such a VOL. 9

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brightness of Si NCs.47 The highly controlled H-terminated surfaces of the Si NCs of widely tunable size provide effective models for deeper understanding of capping ligand chemistry on Si NC surfaces. Although ligand-capped Si NCs cannot yet be made effectively with widely tunable size and high yields by colloidal arrested precipitation routes, Si nanorods and nanowires with these properties can be created (Figure 1CG). In these reactions, metal seeds are added to promote the crystallization of Si at relatively low temperatures. For example, Si nanowires can be grown using Au NCs as crystallization seeds and catalysts in supercritical toluene at ∼490 C using diphenylsilane as a reactant52 or at lower temperature in a high boiling solvent like octacosane, using more reactive trisilane.53 This approach, based on the vapor liquidsolid mechanism described by Wagner and Ellis in 1964, can be effectively employed in solutionphase reactions (known as solution liquidsolid (SLS) growth), as demonstrated by Buhro for Group IIIV semiconductors in 1995.54,55 When capping ligands (dodecylamine) were added to SLS reactions with trisilane reactant, much shorter and narrower diameter Si nanorods could be obtained from colloidal reactions in high boiling solvents, such as squalane, at ∼400 C using either Au51 or lower-melting Sn.20 Nanorods with diameters less than 4 nm can be obtained, which is small enough for quantum confinement. Using this approach, Si nanorods have now been produced with relatively bright photoluminesce (with quantum yields >5%). This was enabled by the use of Sn as a seed metal, followed by a controlled surface etch to remove the Sn seeds and a native oxide layer and then a hydrosilylation passivation of the nanorods.20 Auseeded Si nanorods were found to be dark, even after etching away the Au seeds,56 due to Au contamination of the Si nanorod core. The Si nanorod synthesis has been further simplified to a single-step reaction in VOL. 9

which a Sn reactant is combined with trisilane in a reaction mixture before hot injection into the reaction solvent.21 Trisilane serves as a reducing agent to form the Sn seed particles that promote nanorod growth in situ in the reaction. Perhaps this approach might yield a direct arrested precipitation of Si NCs, essentially via the addition of a crystallization catalyst to enable high yields of crystalline particles at relatively low synthesis temperatures. Apart from light emission, Si nanomaterials are being explored for other applications. One particularly promising application for solution-grown Si nanowires is to use them as electrode materials in lithium ion batteries (LIBs) as replacements for the graphite anode. Silicon spontaneously lithiates at room temperature and has 10 times the lithium charge storage capacity of graphite. Silicon, however, also expands by almost 300% in volume when it is fully lithiated, and thus nanostructures are required to tolerate this expansion and provide stable and reliable battery performance. One challenge with Si is that it is electrically insulating, and in reasonably thick Si electrodes in LIBs, poor electrical conductivity becomes a major limitation.57 By manipulating the Si nanowire chemistry, this problem can be overcome either by creating a thin carbon skin on the Si nanowires that serves as a conductive pathway for charge transport57,58 or by incorporating large amounts of Sn (up to 10%) in Si nanowires,59 which is well above the solubility limit of Sn in Si. These Si-based nanomaterials have exhibited relatively high charge storage capacities (∼1000 mA h g1) at high charging rates of 1C. We will provide further discussion on the use of colloidal nanomaterials in rechargeable batteries later in this Nano Focus. Multinary (Ternary, Quaternary, etc.) Non-Heavy-Metal Chalcogenides. Colloidal NCs with increasingly large numbers of elements and nanoheterostructures with gradually higher levels of sophistication are being ’

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from the silica host by etching and then by passivating with a capping ligand layer by hydrosilylation with alkenes. This approach has been used to produce Si NCs with sizetunable photoluminescence with relatively high quantum yields across a wide range of wavelengths.46 Ligand-stabilized Si NCs with nearinfrared photoluminescence (PL) quantum yields of over 40% have been produced using this route.47 This synthetic approach can also provide ligand-stabilized Si NCs with extremely narrow size distributions and has enabled the first examples of colloidal Si NC superlattices (Figure 1A,B).19 The strong covalent SiC bonding between the Si core and the alkyl capping ligands provides a new class of extremely thermally stable ligand-capped NCs, with decomposition temperatures that are more than 150 C higher than those of dodecanethiol-capped gold NCs, for example.48 These Si NCs obtained from HSQ decomposition also serve as an effective model system to create a better understanding of the surface reactivity and capping ligand chemistry of Si, which is needed if a direct arrested precipitation method is ever to be developed. After the host matrix is etched, Si NCs are obtained with a H-terminated surface, which can then be used as a platform for carrying out controlled surface passivation reactions. Although there is extensive understanding of surface modification chemistry of Si surfaces, NCs have exhibited some surprisingly new reaction chemistry due to their highly curved surfaces. For example, room temperature hydrosilylation has been demonstrated on small (1200 nm were obtained by electrochemically controlling the NPs' carrier concentration by almost a factor of 3. By embedding plasmonic ITO NCs in an amorphous niobium oxide matrix,233 nanocomposites were created that can dynamically control near-infrared and visible light transmittance independently as a function of the applied electrochemical voltage (Figure 10b).235 Coatings of these nanocomposites switch progressively between three KOVALENKO ET AL.

and a route to design n-type and p-type semiconductors for integration in low-cost, large-area electronic, optoelectronic, and thermoelectric devices. Charge transport in semiconductor NC solids has advanced from early foundational measurements of dark and photoconductivity, using solid-state and electrochemical platforms.333335 Today, high-mobility, high-conductivity charge transport has been reported with electron mobilities of >10 cm2/Vs and hole mobilities of >1 cm2/Vs in IIVI,240,336 IIIV,337 and IVVI239,338,339 semiconductor NC solids, using electrical measurements in the field-effect transistor239,240,336,337 (Figure 11) and Hall geometries227,340 and in timeresolved microwave conductivity measurements.338 This high-mobility charge transport has been achieved by (i) taking advantage of the synthesis of monodisperse NC building blocks to reduce site-to-site energy dispersion; (ii) strong electronic coupling, through exchange of the ligands used in synthesis with the compact ligand chemistries described above; and (iii) doping and passivation at the NC surface, by introducing extrinsic atoms (e.g., indium in CdSe NC solids),240,336 additional atoms to shift the NC stoichiometry (e.g., excess metal or chalcogen in IIVI and IVVI solids),339,341344 ligands (e.g., halides),345,346 and oxide layers (e.g.,

optical states: fully transparent, selectively near-infrared blocking, and broad-band blocking of visible and infrared light. It should also be noted that the modest visible light modulation in the pure material of the amorphous matrix, the NbOx, was increased by a factor of 5 by the incorporation of the NCs into the glass composite, with an optimal NC content of about 40%. This enhancement of the optical contrast in the visible spectral region was attributed to structural reconstruction of the NbOx matrix, as a consequence of the covalent linkage to the embedded NCs. This high electrochromic response of the NCglass nanocomposite could enable energy-saving “smart” windows that uniquely manage thermal loads and daylighting in buildings, cars, aircrafts, ships, and so on. The responsive nature of metal oxide NC plasmons will undoubtedly find additional applications in the near future. For instance, these NCs could be deployed in biological environments to sense and mediate redox events. Building Nanocrystal-Based Electronics. Colloidal semiconductor NCs introduce a new, solution-based material class from which solid-state electronic materials can be assembled. These assembled NC solids provide a playground to probe the collective interactions that give rise to charge transport in solid-state materials VOL. 9

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Figure 10. (a) Extinction spectra of various doped oxide nanocrystals demonstrating the synthetic tunability of their localized surface plasmon resonances. (i,ii) Tin-doped indium oxide, (iii,iv) indium-doped cadmium oxide, and (v,vi) aluminum-doped zinc oxide with different doping levels are shown. Reprinted from ref 324. Copyright 2014 American Chemical Society. (b) Dynamic modulation of near-infrared and visible light transmittance by an ITO-in-niobia nanocomposite film under applied electrochemical potential. Reprinted from ref 332. Copyright 2013 American Chemical Society.

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Figure 11. (a) Schematic and (b) transfer characteristics in the linear and saturation regimes of a thiocyanate-exchanged, solution-deposited, CdSe nanocrystal transistor fabricated on a flexible Kapton substrate. (c) Photograph and (d) output characteristics of five-stage, CdSe NC-integrated circuit ring oscillator. Reprinted with permission from ref 350. Copyright 2012 Nature Publishing Group.

Al2O3)239,347 either during or postsynthesis and using solution and physical vapor deposition methods. The combination of strong coupling, doping, and passivation enables control over the carrier type, concentration, and mobility; the trap density and energy; and, therefore, the Fermi energy in NC solids, which is important for device design. There are still remaining opportunities to improve charge transport in NC solids. For example, while there is early evidence of small domains of ordering in lead chalcogenide NC solids, long-range order promises improved charge transport by overcoming Anderson localization.342,348 The most stable, highmobility NC solids are realized for metal-rich and halide-passivated NC surfaces that yield n-type NC solids. Development of comparable p-doped materials is important to improve the performance of NCbased devices, most notably to fabricate pn junctions or complementary metal oxide semiconductor (CMOS) circuits with balanced electron and hole transport. These high-mobility semiconductor NC solids have been incorporated into electronic and optoelectronic devices. The noncorrosive, lowtemperature processing used to form high-mobility NC solids has enabled their fabrication on flexible KOVALENKO ET AL.

plastics.349 For example, Figure 11a, b shows the device schematic and transfer characteristics of an n-type CdSe NC field-effect transistor constructed on flexible Kapton substrates.350 This device geometry has been scaled to enable device operation at low voltages. These flexible NC FETs have been integrated into circuitry by fabricating vertical interconnect access holes to connect device terminals and construct n-type metal oxide semiconductor field-effect transistor (MOSFET) analogues and digital NC-based electronics. Figure 11c,d shows a photograph and output characteristics of a five-stage, NC-integrated circuit ring oscillator, composed of 10 transistors to form the oscillator and two additional transistors that serve as a buffer. All NC FETs across the 2 cm 6 cm substrate have similar device parameters to enable their operation in concert as a ring oscillator. Recent demonstrations of NC device fabrication using common cleanroom techniques351 allow the device dimensions to be scaled down and suggest that future large-area, complex, higher bandwidth, and higher speed analog and digital NC-based circuits are feasible. Encapsulation of NC devices by atomic layer deposition improves the device performance, which is important for circuitry and enables device operation VOL. 9

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in ambient air.239,351 Nanocrystals are emerging as a promising material class for low-cost, large-area, and flexible electronic circuitry. Opportunities to improve circuit speed, to decrease power, and to decrease noise may be realized through advances in material, device, and circuit design, fabrication, and characterization. Furthermore, it was recently found that, when films of surfactantcoated NCs are irradiated with an electron beam or with X-rays, they become inert toward cation exchange.352 Initial studies have indicated that irradiation cross-links the ligands at the surface of the NCs to the extent that a cross-linked ligand shell creates a barrier to the flow of ions to/from the NCs. This enables the patterning of NC films into chemically different components with different physical properties by locally (that is, in the irradiated regions) inhibiting cation exchange. This “masked” cation exchange process can, in principle, be employed to fabricate electrical circuits in NC films with no alteration of their initial morphology.

Nanocrystals are emerging as a promising material class for lowcost, large-area, and flexible electronic circuitry. Nanocrystal Quantum Dots with Engineered Interfaces for Light-Emitting Diodes. The improvement in lighting efficiency is an important element of today's energy-saving strategies. One approach toward more efficient lighting involves the use of LEDs where electric current is directly converted into a stream of photons. Chemically synthesized QDs have emerged as a new promising class of materials for low-cost yet efficient LEDs.35,353 Quantum dot LEDs have advanced tremendously over the past two decades, evolving from proof-ofprinciple polymerQD structures354 ’

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NANO FOCUS Figure 12. QD-based light-emitting diodes.361 (a) Inverted LED comprising an active layer of engineered QDs contacted by electron (bottom) and hole (top) transport/injection layers. The bottom contact is based on zinc oxide (ZnO) nanoparticles deposited onto indium tin oxide; the top contact is based on 4,40 -bis(N-carbazolyl)-1,10 -biphenyl on aluminum capped with molybdenum oxide. (b) Energy band diagram of the inverted QD-LED with an active emitting layer based on CdSe/CdSexS1x/ CdS QDs with an alloyed interface. (c) External quantum efficiency (EQE) versus current density for two QD-LEDs: one employing CdSe/CdS QDs with an abrupt interface (black diamonds) and the other, CdSe/CdSexS1x/CdS QDs (x is ca. 0.5), with an alloyed interface (red circles). Both samples have the same CdSe core radius (r = 1.5 nm) and the same total radius (R = 7 nm); the thickness of the CdSexS1x alloy layer is 1.5 nm. (d) EQE versus current density of QD-LEDs with CdSe/CdS QDs (r = 1.5 nm and R = 3.5 nm; lower inset and the trace shown by black triangles) and CdSe/CdS/Zn0.5Cd0.5S QDs (r = 1.5 nm, R = 3.5 nm, and the Zn0.5Cd0.5S layer thickness is 1.5 nm; top inset and the trace shown by red circles). Vertical dashed lines indicate EQE roll-off onsets defined as the current density for which EQE drops by one-half (J1/2EQE). Reprinted with permission from ref 361. Copyright 2013 Nature Publishing Group.

to modern devices employing direct charge injection from finely tuned electron and hole transport layers.337,355359 Outstanding challenges in the field of QD-LEDs are associated with still insufficient long-term stability of devices and efficiency losses at high currents (socalled, efficiency roll-off or droop). There is ample evidence that reversible degradation of the LED efficiency at high currents originates from nonradiative Auger recombination, whereby the electronhole recombination energy is not released as a photon but instead dissipates as kinetic energy of the extra carrier.359361 For example, recent studies of inverted LEDs (Figure 12a,b) demonstrate the propensity of these devices to generate excess electrons in the emitting layer.361 As a result, a significant contribution to emission is provided by negatively charged excitons (that is, negative KOVALENKO ET AL.

trions) that are subject to fast Auger recombination.362364 Recently, two approaches have been proposed to mitigate this problem.361,365 The first approach involves the use of thick-shell CdSe/CdS QDs with an intermediate CdSexS1x alloy layer at the coreshell interface, which helps to suppress Auger recombination and thus to increase the emission efficiency of charged species (Figure 12c). As indicated by theoretical modeling366 as well as experimental spectroscopic studies,367 this effect is linked to “smoothing” of the confinement potential, which reduces the matrix element of a nonradiative intraband transition involved in Auger decay. In the second approach, the conduction band edge of a QD is raised using an additional layer of a higher band gap ZnxCd1xS alloy (Figure 12d). This enables one to impede electron injection moderately and thus to VOL. 9

improve the charge-injection balance within the QD active layer. Use of either of these strategies enhances peak emission efficiency (EQE up to 1.8% for the first approach and 7.5% for the second) and also significantly increases the threshold current of efficiency rolloff (Figure 12c,d).361 These studies demonstrate a large promise of interface engineering for optimizing QD performance in LEDs by reducing nonradiative losses associated with Auger recombination. At the same time, for practical applications, the lessons learned from IIVI materials need to be translated to cadmium-free NCs. LASER EMISSION FROM NANOCRYSTAL QUANTUM DOTS Nanocrystal Lasing. Due to high, near-unity emission efficiencies and size-dependent emission wavelengths, ’

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excitonexciton repulsion (on the order of 100 meV), which produced transient displacement of a bandedge absorbing transition away from the emission line in the case when a single exciton was injected into a NC. As a result, population inversion could be realized with single excitons without complications associated with Auger recombination. Several recent efforts have focused on the structures with suppressed Auger recombination. An interesting development in this area has come from the exploitation of CdSe/CdS dot-in-rod NCs, in which the localization of holes in the CdSe core and the substantial delocalization of electrons throughout the whole NC creates a quasi-type-II system,377 which leads to a considerable decrease in the Auger recombination rate379 and, as a result, facilitates ASE. Furthermore, engineering of the CdSe core and of the CdS shell in these NCs allows one to realize ASE from either the core, the shell, or both,374 and the strong confinement of both electrons and holes within the inorganic core leads to an enhanced temperature stability of the ASE threshold, a signature of true QD ASE/lasing.355 The integration of these NCs into microresonators, for example, via the deposition of films of NCs onto silica microspheres380 or the creation of coffee-stain rings of closepacked NC multilayers by selfassembly381,382 has recently paved the way to new concepts of NCbased lasers. Novel prototype lasing devices have recently been fabricated with other types of coreshell NCs (e.g., CdZnS/ZnS).383 Interesting opportunities in the field of NC lasing are associated with the use of 2D nanostructures (nanosheets and nanoplatelets) that have been under active development during the last 23 years. Especially in the case of CdSe, much work has been done to optimize the fabrication of core (i.e., “CdSe” only) and coreshell architectures.384387 The interest in these materials stems from the fact that they can be VOL. 9

considered as the colloidal analogues of epitaxial quantum wells: excitons are strongly confined in one dimension, while the in-plane confinement is much weaker.388 Apart from interesting effects observed in CdSe nanoplatelets, like narrow emission line widths, high fluorescence quantum yields, and ultrafast fluorescence lifetimes, one key aspect distinguishes them from the corresponding CdSe quantum dots (0D) and quantum rods/wires (1D): the quantization of levels only in one direction imposes stricter restrictions on momentum conservation and therefore results in a lower rate of Auger recombination. CdSe and CdSe/CdS nanoplatelets thus represent interesting candidates for the realization of low-threshold (potentially, lower than for quantum dots and rods) ASE and lasing.389391 A significant promise of these materials for lasing applications has been indicated by the recent demonstration of continuous-wave stimulated emission and lasing using closepacked films of colloidal CdSe nanoplatelets.391 Carbon-Based Nanoparticles for LightEmitting Devices. Carbon-based dots (CDs)392 have emerged as an active area of research due to their broadband optical absorption, strong photoluminescence, low toxicity, and high chemical stability. Recently, great progress has been made in the large-scale preparation of CDs by methods such as electrochemical oxidation processes, hydrothermal

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NCs are attractive materials for the realization of highly flexible, solution-processed lasing media. Paradoxically, despite their favorable light-emitting properties, NCs are difficult to use in optical amplification. Because of nearly exact balance between absorption and stimulated emission in NCs excited with single electronhole pairs (single excitons), the condition for optical amplification can only be achieved by exciting two excitons (that is, biexcitons) in at least a fraction of the NCs in the ensemble.368 The resulting complication is associated with nonradiative Auger recombination, which leads to fast optical gain decay. In this process, instead of being emitted as a photon, the electronhole pair recombination energy is transferred to a third carrier (an electron or a hole) on extremely short time scales of tens to hundreds of picoseconds.369,370 To resolve the problem of Auger recombination, the first successful demonstration of amplified spontaneous emission (ASE) from the NCs utilized a short-pulse laser as an excitation source and a dense close-packed NC solid as a gain medium.368 Ultrafast charge carrier injection was essential for avoiding population losses during the pumping stage, while a high density of NC emitters allowed for a fast buildup of ASE, which could compete with Auger decay. After the elucidation of the principal mechanism for optical gain decay, additional progress in NC lasing has been associated with the development of structures with suppressed Auger recombination (e.g., nanorods,371,372 thick-shell CdSe/CdS NCs [“giant” quantum dots],373 or dot-in-rod NCs374) and exploration of novel lasing concepts such as “single-exciton” gain realized in NCs with strong excitonexciton repulsion.375377 The principles of single-exciton gain, originally introduced in ref 375, were implemented practically in ref 378 using type-II CdS/ZnSe NCs. These structures enabled strong

Carbon-based dots have emerged as an active area of research due to their broad-band optical absorption, strong photoluminescence, low toxicity, and high chemical stability.

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NANO FOCUS Figure 13. (a) Absorption and photoluminescence (340 nm excitation wavelength) spectra of carbon-based dots and a TEM/ HRTEM image of CDs. Reprinted from ref 399. Copyright 2013 American Chemical Society. (b) Schematic illustration of the preparation of the CD ionogel using organosilane-functionalized CDs (Si-CDs) through solgel processing in the presence of ionic liquid 1-(3-carboxypropyl)-3-butylimidazolium bromide. (c) Schematic illustration of the light propagation through the increasingly thicker layers of the CD ionogel, resulting in the different emission color as a consequence of multiple light reabsorption and the subsequent emission steps. Reprinted from ref 398. Copyright 2014 American Chemical Society. (d) Current density and brightness of the CD light-emitting diodes (structure shown in inset) emitting blue, cyan, magenta, and white light, with the corresponding electroluminescence (EL) spectra. Reprinted from ref 399. Copyright 2013 American Chemical Society. (e) EL spectra of a white LED fabricated from a mixture of blue-emitting CDs and green and red emitting zinc copper indium sulfide quantum dots, with the corresponding color triangle and a white LED photograph. Reprinted with permission from ref 400. Copyright 2014 AIP Publishing LLC. KOVALENKO ET AL.

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(5%) size dispersion. As discussed above, they afford the possibility of low-cost liquid processing at moderate temperatures, a characteristic shared with organic materials, but with the possibility of sustaining infrared electronic transitions. The first step in exploring their potential as infrared detectors or emitters is therefore to develop colloidal QDs with infrared electronic transitions. These could be interband or intraband, as shown in Figure 14. Intraband transitions in CdSe were the first instance of MWIR electronic transitions in colloidal QDs.403 However, the ultrafast excitonic relaxation404 suggested ultrafast nonradiative intraband relaxation. It is now understood that, in the absence of a multicarrier mechanism or without coupling to the vibrational modes of the ligand shells, slower intraband relaxation can be obtained.405 Another limitation was that an intraband infrared photoresponse requires the precise filling of intraband states, but controlled doping in colloidal quantum dots has remained difficult.406 On the contrary, interband transitions require only an appropriate band gap energy to begin, and the past decade has seen much improvement in making colloidal QDs with infrared interband transitions, first using small gap lead salts407 such as PbSe408 (bulk gap of 0.3 eV) and then HgTe (0 eV gap).409,410 In parallel, the conductivity improvement brought about by ligand exchange after QD film formation411 and the ohmic conductivity412 achieved in such films enabled efficient photoconductivity that evolved from visible to near-IR detection,413416 eventually into the MWIR with HgTe417 and recently into the LWIR.418 The development of HgTe colloidal QDs now focuses on improving the infrared detectivity through the device structure, the material processing, and the emission properties, and it may well lead to a disruptive IR technology. Interest in intraband photoconduction was renewed in the past

and the injecting current density (by changing the applied voltage), multicolor emission of blue, cyan, magenta, and white can be obtained from the same CDs (Figure 13d). By combining CDs that emit blue light and zinc copper indium sulfide QDs that emit in the green and red regions of the electromagnetic spectrum, white LEDs (Figure 13e) with a high color-rendering index of 93 have been realized.400 These examples highlight the promise of CD-based composites with controlled chromaticity photo- and electroluminescence. Future comprehensive studies using ultrafast spectroscopy techniques, linked with the synthetic design of the CDbased hybrid materials at the nanometer scale, will help to elucidate the mechanisms and kinetics of charge transfer and recombination processes in such composites. Material design of CD-based LED devices and carefully engineered LED device structures will lead to optimized, efficient nextgeneration color displays and solid-state lighting. Infrared Photodetectors;From Interband to Intraband. The thermal infrared imaging ranges are the midwave infrared (MWIR, 35 μm) and long-wave infrared (LWIR, 812 μm). Many current infrared devices are based on bulk semiconductor or nanostructured materials grown by epitaxy and cost in excess of $50 000 for cameras, which leaves the door open for disruptive technologies. Infrared semiconductor devices use interband transitions as well as all possible manners of band gap engineering including inter-sub-band transitions with quantum wells or intraband transitions with QDs and type-II structures.401 Epitaxial QDs should have significant advantages due to the expected slower carrier relaxation compared to wells,402 but the epitaxial QD devices realized so far have remained inferior to the bulk technology. Colloidal QDs show promise because they can be assembled as close-packed solids and with narrow VOL. 9

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scission strategies, chemical oxidation methods, and carbonizing organic precursor syntheses. These low-cost, mild, and green synthetic methods have also served as a platform for further manipulation of their properties, enabling customized design of novel functional materials. Reported by Sun et al. in 2006,393 these fluorophores combine several attributes of traditional semiconductor QDs such as tunable luminescence emission and high resistance to photobleaching without incurring the burden of intrinsic toxicity or being hostage to elemental scarcity. In recent years, CDs have been demonstrated to possess high (up to 6080%) emission quantum yields394,395 in the blue spectral region (Figure 13a), making them competitive in light-emitting performance with QDs. Several reports have shown that the efficient and excitation-dependent photo- and electroluminescence of CDs is promising in the fabrication of hybrid LEDs and thus has potential applications for displays and solidstate lighting.396,397 It was recently shown398 how the surfaces of CDs can be functionalized with organosilanes and incorporated into highly flexible hybrid materials when combined with ionic liquids within silica gel networks to form CD ionogels (Figure 13b) with properties that are promising for the fabrication of flexible displays and other optical technologies. The emission from such CD ionogels can be tuned across a large range of the CIE display gamut as a result of the sequential multiple light reabsorption and subsequent emission, resulting in the thicknessdependent red shift of the emitted light (Figure 13c) and, thus, fullcolor performance. Furthermore, CD-based LEDs with driving-current-controlled color change were introduced.399 These devices consist of a CD emissive layer sandwiched between an organic hole transport layer and an organic or inorganic electron transport layer fabricated by solution processing (Figure 13d). By tuning the device structure

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Figure 14. Possible schemes for obtaining infrared electronic absorption in singlecomponent colloidal quantum dots. The intraband scheme allows the use of wide band gap semiconductors if they can be doped. They could then be transparent in the visible and absorbing in the IR, which is potentially useful for enhanced vision. The interband scheme relies on small gap semiconductors. One could also envision coreshell nanocrystals of type-II structures.

Figure 15. Photocurrent of films of HgTe and n-HgSe colloidal quantum dots of ∼15 and ∼6 nm, respectively. The films are deposited on interdigitated electrodes and treated in air with ethanedithiol. The measurements are done at 80 K. The intraband photoresponse of n-HgSe just covers the midwave infrared. Reprinted from ref 419. Copyright 2014 American Chemical Society.

year with the discovery of air-stable n-doping of β-HgS QDs.420 Indeed, β-HgS QDs exhibit a surface-tunable occupation of the lowest 1Se conduction band state with a strong absorption and weak luminescence of the 1Se1Pe intraband transition in the MWIR. The same properties were also observed for HgSe QDs, which can be made with better size control. As a result of the stable doping, colloidal HgS and HgSe QD intraband photodetectors have recently been demonstrated in the MWIR, and their best performance is similar to the best interband detectors at similar wavelengths.419 Figure 15 shows photocurrent spectra taken with interband HgTe and intraband HgSe. Both systems show similar signal-to-noise ratios, KOVALENKO ET AL.

but the intraband response is much narrower, being restricted to the 1Se1Pe transition. When other systems are successfully doped with carriers, intraband devices may allow the use of wider gap semiconductors for infrared applications, such as using n-ZnO or n-CdS. Using either interband or intraband transitions, colloidal QDs have interesting infrared properties for infrared detection or emission. The n-HgSe QDs' intraband photodetector is also conceptually significant since it is the first instance of using the intraband transitions of a colloidal semiconductor structure, and one can now add the intraband transitions to the range of colloidal QD design. Hybrid Two- and Zero-Dimensional Quantum Dot Photodetectors. Colloidal VOL. 9

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QD photodetectors have seen tremendous progress over the past decade and have emerged as a novel sensing platform for high sensitivity, low-cost photodetectors, whose spectral coverage can readily extend from the UV to the shortwave and mid-IR spectrum.414,421424 Photoconductive detectors414,421 and photodiodes422 based on QDs have both been reported, showing distinct exciting features: photodiodes are detectors with fast response (determined by the transit time of carriers) and responsivity that cannot exceed the 100% quantum efficiency limit; on the other hand, photoconductive detectors have shown significant photoconductive gain on the order of 103 or higher, determined by the ratio of carrier lifetime over carrier transit time. Photoconductive detectors tend to be slower in time response, as determined by the carrier lifetime, but they offer significant promise for sensing with higher sensitivity because they have the potential to overcome the read-out noise floor. Improving the performance of photoconductive detectors will rely on two advances: (1) identifying material processing methods that introduce shallower trap states/sensitizing centers to accelerate the carrier lifetime and thereby the temporal response of the detector,425 and (2) decreasing the transit correspondingly to account for the reduction of lifetime so that gain is not considerably affected. Significant efforts have been undertaken to increase carrier mobility in colloidal QD solids and have reached impressive values of 1030 cm2/Vs.238 The mobility values, however, still fall well below the ones met in singlecrystalline counterparts. A potential solution to this road block was recently demonstrated by exploiting the synergism of colloidal QDs with graphene. Colloidal QDs offer unprecedented opportunities to tailor optical absorption across a broad range, whereas graphene provides carrier mobilities that cannot be matched in any other

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NANO FOCUS Figure 16. High-gain, high-sensitivity graphenequantum dot photodetectors. (a) Device structure of the grapheneQD phototransistor. (b) Band alignment at the graphenePbS QD interface. (c) Spectral responsivity of QDgraphene phototransistors employing two different sizes of QDs to cover the visNIR (top panel) and SWIRvis (bottom panel) parts of the spectrum. The achieved responsivities in both cases are in excess of 106 A/W. Reprinted with permission from ref 428. Copyright 2012 Nature Publishing Group.

Colloidal QD photodetectors have seen tremendous progress over the past decade and have emerged as a novel sensing platform for high sensitivity, lowcost photodetectors, whose spectral coverage can readily extend from the UV to the shortwave and mid-IR spectrum.

single-crystalline or nanocrystalline material.426,427 It was recently shown that efficient charge transfer of photogenerated carriers in a QD solid placed atop a graphene transistor offers an advantageous platform for achieving record gains (on the order of 107) as a result of the prolonged carrier lifetime in the QD layer and the ultrahigh mobility (on the order of 5001000 cm2/Vs) of the graphene channel.428 In this KOVALENKO ET AL.

architecture (Figure 16a), the QD layer acts as an efficient sensitizer for graphene in which photogenerated holes are transferred to the graphene channel, whereas electrons remain trapped in the QD layer (Figure 16b). With an applied electric field, holes recirculate within the graphene channel as long as the electrons remain in the colloidal QD layer. This gain was achieved with low applied electric fields, on the order of 103 V/cm, and both material platforms are fully compatible with large-area manufacturing and CMOS processing, opening the way toward monolithic integration to CMOS or flexible electronic technologies to cover both the visible and infrared spectra (Figure 16c). The presence of the back-gate electrode also offers additional functionalities, as it can electrostatically modulate the band alignment of the grapheneQD interface and therefore acts as a local electric knob that can tune gain in this transistor from its maximum value to zero, offering the possibility of resetting the detector. At present, one of the major challenges is the existence of a high dark current due to the lack of a band gap in graphene. However, a new realm of opportunities has emerged with the advent of other 2D semiconductors that enable high VOL. 9

in-plane carrier mobilities at atomically thin layers with the added benefit of the presence of a band gap.429 The latter enables control of the carrier density in the channel over a much broader range; as a result, similarly performing photodetectors with significantly lower dark current rates are within reach. Further co-optimization of the integrated amplification stage offered by the 2D channel with the sensitizing photogating CQD layer may pave the way for achieving even higher performance in sensitivity and functionalities offered by this hybrid platform. Novel Architectures for Colloidal Nanocrystal Solar Cells Based on Inorganic Bulk Heterojunctions. Quantum dot solar cells have emerged as one of the most promising technologies for solution-processed thin-film photovoltaics, leveraging their solution processing and facile band gap tunability.430 The latter possibility has been a major driving force toward third-generation photovoltaics, as well, exploiting both multiple exciton generation effects431 and the development of tandem solar cells.432 Recent advances in the control of surface passivation have led to dramatic performance improvement in power conversion efficiencies, now reported to reach nearly ’

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been shown that majority electrons from ZnO NCs can be utilized to fill electron trap states in PbS QDs when the bulk heterojunction of ZnO and PbS NCs is employed.438 This may enable both new remote passivation techniques for colloidal NC materials for which atomic/ligand passivation schemes may not be available and also engineered properties of NC composites at the supra-nanocrystalline level. Last but not least, the presence of a distributed heterojunction at the nanoscale may potentially expand the available quantum-confined materials whose exciton binding energy has been prohibitively high for their use in bilayer heterojunction arhictectures (e.g., CIS(Se) QDs). Carrier Multiplication for High-Efficiency Solar Cells. Semiconductor NCs offer a number of functionalities that are attractive for solar energy conversion. A size-controlled tunable band gap in combination with lowtemperature synthesis and processing can enable low-cost, highefficiency single- and multiplejunction PV cells based on NCs of various formulations and sizes.439442 High emission efficiencies and tunable emission colors along with a large engineered Stokes shift can help to realize new types of luminescent solar concentrators and new schemes for spectral reshaping of solar radiation.443445 Attractive prospects are also associated with use of novel processes such as carrier multiplication (CM) for boosting PV efficiencies above traditional thermodynamic limits.446448 CM is a process by which absorption of a single photon produces multiple electronhole pairs (excitons). It can potentially increase the power conversion efficiency of single-junction PVs to above 40% via increased photocurrent.449,450 The first spectroscopic observation of CM in PbSe NCs451 and follow-up studies of this process in NCs of various compositions452457 have demonstrated that CM can indeed be enhanced in nanomaterials compared to bulk solids. This assessment is based

is an eminent need to explore alternative semiconductor compounds for use in environmentally friendly green photovoltaics (PVs). Some of the key features that have led to successful employment of PbS QDs in solar cells include its large dielectric constant and therefore small exciton binding energy that allows exciton dissociation at room temperature in the absence of a junction, its favorably long carrier lifetime that can effectively compete with the currently achieved carrier mobilities for efficient charge collection, and its mild doping that allows the formation of depletion widths in excess of 200 nm. Caution is therefore required, as alternative semiconductor materials may not possess such features. The employment of traditional planar heterojunctions may not serve as a promising architecture for high-efficiency NC solar cells. Recently, and following the paradigm of polymerbased solar cells, the introduction of bulk heterojunctions for inorganic NC solar cells has been shown to be a novel architectural platform for QD and NC solar cells.437 In this architecture, the photoactive layer consists of two types of NCs, an n-type electron acceptor and a p-type electron donor material, that have been blended on the nanoscale so that the charge separation interface is extended throughout the bulk heterojunction (Figure 17a). One of the key aspects of this approach is that charge transfer of minority carriers to the corresponding collecting medium takes place at the nanoscale, suppressing minority carrier transport, and leads to a significant increase in effective carrier lifetime and, consequently, to charge collection efficiency (Figure 17b). The employment of an inorganic bulk heterojunction has also enabled remote trap passivation in QD solar cells, resulting in higher open circuit voltages as a result of suppressed trap-assisted recombination (Figure 17c). Similar to the advanced atomic passivation techniques previously employed, it has VOL. 9

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9%.433436 These improvements are the result of tuning the surface properties of QDs in order to passivate deep traps with reflected effects on improved carrier mobility and suppressed trap-recombination.434,435 Modification of the surface dipole moment has also been suggested as a novel strategy to tune the band energy levels of QD solids and has been shown to result in highly efficient heterojunction QD solar cells.436 Tailoring the electronic properties of QD solids, in particular, controlling doping, has been considered a major challenge, as robust doping techniques had remained elusive. Multiple recent reports have shown that transforming p-type PbS QDs into an n-type electron acceptor material is now within reach. This has been demonstrated both by controlling the cationanion stoichiometry, employment of monovalent halide anions replacing surface sulfur atoms, as well as through employment of heterovalent cations that replace Pb.373,374 The last two approaches have been successfully demonstrated in operational QD hom*ojunction solar cells, and the cation substitution has also yielded robust n-type PbS QDs under extended exposure to air.363 This avenue is expected to pave the way toward advanced design methodologies for controlling the electronic properties of QDs at the atomic level and advanced QD functionalities including intraband transition-based applications. Key challenges that remain include understanding the introduction of dopants in QDs, their incorporation into the crystal structure, and the alleviation of adverse effects that this may have in terms of introducing additional states within the band gap. Advanced codoping/passivation techniques need to be sought to unleash the potential of atomically engineered QD solids. At present, the main body of work on high-performance QD solar cells has been based on PbS QDs. The presence of Pb may pose environmental concerns; therefore, there

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Figure 17. More efficient charge collection and suppressed trap recombination in colloidal quantum dot solar cells is achieved by means of a bulk nano-heterojunction structure in which p-type and n-type materials are blended on the nanometer scale. (a) Schematic of the bilayer (left) and the bulk nano-heterojunction solar cell devices (right) consisting of n-type ZnO nanocrystals and p-type PbS QDs. The improved performance of the heterojunction devices, compared with that of bilayer devices, is displayed in higher photocurrents (b) and higher open circuit voltages (c) (resulting from a trap passivation mechanism at the suprananocrystalline level). Reprinted with permission from ref 438. Copyright 2014 John Wiley and Sons.

on the observed reduction of both the spectral onset of this effect (CM threshold; pωth) and the electron hole (eh) pair creation energy (εeh), that is, the energy in excess of pωth required to create an extra exciton. Other types of nanostructures including quasi-1D nanorods458,459 and 1D carbon nanotubes460 as well as quasi-2D nanoplatelets461 and 2D graphene462 have also shown significant CM efficiencies. Furthermore, studies of QD-based devices such as photodetectors423 and PV cells431,463 have demonstrated that CM can produce greater-than-unity KOVALENKO ET AL.

quantum efficiencies in a generated photocurrent, which firmly establishes the relevance of this phenomenon to practical solar energy conversion technologies. A current challenge in the CM field is the development of structures operating at or near the limit defined by energy conservation. As applied to the CM threshold and the eh pair creation energy, the corresponding targets are εeh = Eg and pωth = 2Eg. A “window-ofopportunity” model43 relates εeh to the non-CM (e.g., phonon-related) energy loss rate (kcool; energy VOL. 9

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dissipated per unity time) and the CM rate (rCM = 1/τCM; τCM is the characteristic CM time) by εeh = kcool/rCM = kcoolτCM. Hence a smaller εeh can be achieved by either increasing the CM rate or decreasing the cooling rate. Recently, the role of intraband cooling in CM was evaluated via a comparative study of PbS, PbSe, and PbTe QDs.43,75,76 These studies indicated that the measured CM yields are directly correlated with the energy loss rates inferred either from direct measurements of intraband relaxation or from estimated phonon emission rates. This suggested the possibility of enhancing CM yields by designing NCs with slowed intraband cooling. The concept of “cooling-rate engineering” was recently tested by Cirloganu et al. using PbSe/CdSe coreshell QDs with exceptionally thick shells (Figure 18a).464 Theoretical modeling of these structures indicates that a large valence band offset between PbSe and CdSe (Figure 18b) and a significant disparity between hole masses lead to strong backscattering of hole wave functions at the PbSe/CdSe interface. Therefore, at large shell thicknesses and correspondingly large aspect ratios (F, defined as the ratio between the shell thickness and the total NC radius), the higher energy holes are almost entirely shelllocalized, while the lower energy states remain primarily confined to the core. As a result, these two types of states become electronically decoupled, which is further emphasized by a sizable energetic gap separating them at large F (Figure 18b). These effects are expected to slow the cooling of a “hot” shell-localized hole, which, in turn, should enhance the CM channel associated with scattering of this long-lived energetic hole with a preexisting electron in the band-edge core-localized states (Figure 18b). A prominent signature of reduced rates of hole cooling was the observation of shell-related PL in the visible spectrum, which emerged for

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NANO FOCUS Figure 18. Thick-shell PbSe/CdSe nanocrystals with enhanced carrier multiplication yields.464 (a) TEM image of a sample of PbSe/CdSe NCs with an overall radius of 4 nm and an aspect ratio of 0.52 (10 nm scale bar). Inset: Higher-resolution image of an individual NC (2 nm scale bar). (b) Approximate structure of electronic states for the NC with a 2 nm core radius and a 2 nm shell thickness. The quantum dot energy spectrum features closely spaced electron levels and sparsely distributed hole core levels. Relaxation of a hot hole from a shell-based state to a core-localized level can happen either via a CM process (straight black lines) or by thermalization (dotted black line); the photogenerated and pre-existing carriers are shown by solid and dashed circles, respectively. (c) Photoluminescence spectra of the PbSe/CdSe NCs with aspect ratios of 0.27, 0.4, and 0.52 and a constant overall radius of 4 nm, showing progressive blue shifts with increasing shell size and the emergence of visible emission for the NCs with the thickest shell (shaded spectra); all IR spectra are normalized, while for the thick shell structure, the visible emission amplitude is multiplied by a factor of 60 for the purpose of comparison. Inset: Schematic representation of the band structure indicating the transitions associated with the IR and visible emission. (d) Multiexciton yields measured for PbSe/ CdSe core/shell structures with progressively increasing shell thicknesses (3.1 eV excitation). The QDs have slightly different total sizes but similar band gaps (∼0.87 eV) for proper comparison and are represented by different color squares on the plot (black dashed line is a guide for the eye). The region where energy conservation is met and simultaneously slow cooling is observed (green shading) corresponds to the highest CM yields. The CM yields for core-only PbSe QDs and PbSe nanorods of similar band gaps are shown by the black square and the blue star, respectively.

large aspect ratios of about 0.40.5 (Figure 18c). The appearance of this new emission band correlated with a sharp, almost 4-fold increase of the CM yield (Figure 18d). Specifically, the studies of the PbSe/CdSe NC samples with similar band gaps (0.87 ( 0.02 eV) but different aspect ratios revealed the increase in the CM yield from ∼20% for the coreonly samples (F = 0) to ∼75% for the coreshell NCs with F = 0.68. The measurements of CM efficiency as a function of photon energy also KOVALENKO ET AL.

indicated a considerable reduction of the CM onset almost down the fundamental 2Eg limit.464 These findings suggest that the control of intraband cooling in combination with other demonstrated approaches for enhancing CM yields, such as shape control459 and/or use of semiconductors with reduced rates of phonon emission (e.g., PbTe),465 might provide a practical route for reaching the ideal energyconservation-defined limit in the CM performance. VOL. 9

Theranostic Applications of Nanocrystals. Recently, NCs have been discussed frequently in the context of theranostics. Theranostics involves a platform combining medical diagnostics/analysis with subsequent treatment. From the materials point of view, NCs exhibit significant potential because many different functionalities can be combined in one NC. Nanocrystals comprise an inorganic crystalline core (which can contain coreshell structures such as in the case of CdSe/ZnS) and, in ’

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shapes.473,474 Thus, SPIONs fulfill theranostic purposes, first, by helping to diagnose tumor tissue by providing contrast in MRI to visualize it and, second, by facilitating therapy (i.e., tumor ablation) by local hyperthermia. Similar principles can be extended to more complex applications. Nanocrystals, such as SPIONs, with ion-sensitive fluorophores integrated into their organic surface coating can optically quantify local ion concentrations.475 Upon local creation of heat, SPIONs can also be used to gate ion channels and thus to control ion concentrations.476 The same NCs can both detect irregularities in ion concentration (via integrated ionsensitive fluorophores) and correct them via heat-mediated control of ion channels. In addition to ions, this idea has been indicated for glucose. Again, glucose-sensitive fluorophores on the NC surface could report local glucose concentration,477 and upon diagnosis of increased glucose levels, the levels could be corrected therapeutically by triggering release of insulin via local hyperthermia.478 The above-mentioned examples are based on particles that report data for diagnosis to a physician (e.g., images of tissue, local analyte concentrations) and can, upon switching on an external trigger (e.g., local exposure to alternating magnetic fields), initiate treatment. However, one can also envisage NCs with a direct feedback loop. In such stimuli-responsive NCs, a local trigger (i.e., diagnosis) would transform the properties of the NCs, thus leading to a therapeutic effect. One example is pH-sensitive NCs, which, upon exposure to acidic tumor tissue (diagnosis), locally release drug molecules against the tumor (therapy). Analogous to this approach, pH-sensitive, magnetic, so-called “nanogrenades” (NGs), which are self-assembled NPs composed of iron oxide NPs immobilized in a pH-sensitive polymer, were recently fabricated as theranostic anticancer agents.479 Based VOL. 9

on pH-dependent assembly/ disassembly, magnetic resonance imaging and the photodynamic activity are enhanced when these NGs are present in the tumor environment, where the pH value is lower than elsewhere. Small tumors of only 3 mm implanted in mice were successfully visualized via pHresponsive T1 magnetic resonance and fluorescence imaging, demonstrating early stage diagnosis of tumors.479 Furthermore, the pHtriggered generation of singlet oxygen enabled pH-dependent photodynamic therapy to kill the cancer cells selectively. The enhanced photoactivation of the NGs within the tumor parenchyma enabled superior photodynamic therapeutic efficacy in both human colorectal carcinoma xenografts and in highly drug-resistant heterogeneous tumors. For this purpose, a tumor pH-sensitive nanoformulated triptolide coated with folate targeting ligands was synthesized to treat hepatocellular carcinoma (HCC), which has one of the worst prognoses for survival as it is poorly responsive to both conventional chemotherapy and mechanism-directed therapy (Figure 19).480 Screening hundreds of compounds against a panel of HCC cells showed that triptolide, a natural product, is much more effective than the current standards of therapy. However, its poor solubility and high toxicity prevented triptolide from potential clinical application. Incorporating triptolide into pH-sensitive polymer NPs coated with folate-targeting ligands led to greatly increased progression-free survival in mice with mitigated side effects. All of these examples demonstrate that, from the materials point of view, NCs and NPs are capable of combining diagnostic and therapeutic function in one entity. However, there is still almost no clinical use of theranostic NCs. Setting aside the problem of potential cytotoxic effects, the main hurdle is targeting. NCs enable passive tumor targeting governed by the ’

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the context of biological environments, an organic coating (either by design or by adsorption of proteins).466 Thus, even when the inorganic NC cores act only as passive carriers, the possibility to link different functional molecules to their organic surface coating enables multifunctionality straightforwardly. Functional molecules may involve ligands for specific targeting, for reducing interactions with the immune system, and for providing contrast for imaging, etc. However, the NC cores may also introduce functionality, such as fluorescence, super-paramagnetism, or plasmon resonance. Thus, with inorganic cores and organic shells together, NCs are suitable for combining different functionalities. For example, by combining fluorescent, magnetic, or radioactive cores with fluorescent, magnetic, or radioactive shells, NCs that can be detected with several imaging modalities such as fluorescence microscopy, magnetic resonance imaging (MRI), or single-photon emission computed tomography were demonstrated.467470 In order to be truly theranostic, NCs would need to comprise sensing as well as actuating capabilities. In principle, such NCs are available, such as super-paramagnetic iron oxide NPs (SPIONs). Super-paramagnetic iron oxide NPs can be used as T2 contrast agents for MRI, for example, to indicate the presence of tumors.336 In the same manner, upon irradiation with alternating magnetic fields, SPIONs can also be used to heat locally and thus to destroy tumor tissue by hyperthermia.471 Efforts in this direction are aimed at preparing SPIONs that are optimized for hyperthermia, that is, characterized by high values of specific absorption rates in order to minimize the NP dose to be administered and, therefore, to reduce toxic side effects. In this context, successful approaches have been demonstrated in terms of exchange-coupled coreshell architectures472 and optimized

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size and the enhanced permeation and retention effect.481 This effect is dominant in mice but less pronounced in humans; thus, passive targeting often is not sufficient and involves significant side effects, such as clearance of the NCs by the immune system, leading to their accumulation in the liver. Active targeting of NCs, for example, by the attachment of ligands specific to the target tissue, however, adds little specificity on top of passive targeting.482 Thus, controlled biodistribution is one key issue that remains to be resolved. The general problem to solve is not in the functionality of the materials but rather the basic issue of many pharmaceutical agents: targeted biodistribution. Having made this statement, one has to question critically some recent developments concerning the design of theranostic NCs. In the literature, there are increased reports combining as many functional properties into one NC as possible. However, in many reports, the usefulness of all these different components is not demonstrated. Are all these functions needed? Are the effects of the respective functionalities additive, or is the synergistic effect negligible? To justify the integration of many functionalities into one NC, one would first have to investigate experimentally the effects of all functionalities individually, KOVALENKO ET AL.

then paired functionalities, etc., and finally benchmark the NC with all combined functionalities. Unfortunately, in many reports, authors do not undertake this effort, and thus the practical use of multifunctionality remains in question. One should also keep in mind that, for clinical use, each theranostic NC-based system should be kept as simple as possible. There is no doubt that NCs are well-suited to offer multifunctional properties with the potential for theranostic use. However, in order to translate from laboratory to bedside, one has to go back to solve the basic remaining issues such as biodistribution and biocompatibility,483 instead of aiming only to make the NCs increasingly complex.

of nanosolids composed of NCs as building blocks. In this Nano Focus article, we aimed to provide a snapshot of the current developments and trends in NC research. For more specific information on the topics that we could only briefly discuss here, we refer to recent reviews on NC synthesis,30,33,71,129,323,484489 simulation of NC growth,490 QD photovoltaics,491 QD electronics,492 QD LEDs,493 near- and mid-IR active colloidal QDs,494,417,495 exciton dynamics,496,497 semiconductor NC plasmonics,131,498 surface chemistry,202 biomedical applications of NCs,499 and electrochromic applications of NCs.500 Being at the forefront of NC research, QDs are at an advanced stage of development in terms of the precision of their syntheses as well as control of their surface chemistries. In fact, it is the effect of the surface chemistry on the individual optical properties of QDs and on QD-based optoelectronic devices that will continue to motivate research about inorganic surface capping and simulation of NC surfaces and the enitre NC entity using density functional theory. The advent of inorganically capped NCs was recent, but we foresee it impacting all fields of applications based on NC solids, including electronics, thermoelectrics, and batteries, and triggering a wave of device improvements and new applications

CONCLUSIONS AND OUTLOOK Some tens of years ago, NC research existed as an individual field, with its main focus on the synthesis and basic optical and structural characterization. Contemporary NC research has expanded, impacting many research fields and promising a wide scope of applications, as a broad range of inorganic materials has become accessible in NC form. Topics that unite all researchers dealing with NCs are the advances in synthesis, structural characterization, and surface chemistry; basic optical, magnetic, and electronic properties; and the construction VOL. 9

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Figure 19. Triptolide-based anticancer theranostic nanoparticles for the treatment of hepatocellular carcinoma (HCC). Left: Structure formula of triptolide, a natural bioactive molecule, and schematic of tumor pH-sensitive nanoformulated triptolide, coated with folate, for use in an HCC subpopulation that overexpresses the folate receptor. Right: While triptolide can prevent disease progression, the pH-sensitive nanoformulated triptolide (Nf-Trip) NPs facilitate uptake into the tumor, and specifically tumor cells, leading to increased efficacy while mitigating systemic toxicity, resulting in increased survival rates. Reprinted from ref 480. Copyright 2014 American Chemical Society.

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commercial solar cells and should be addressed in the future. Applications in which the integration of NCs into well-established technologies results in significant improvement in the performance of the latter are certainly beneficial. An example of such an application is the QD color TV, representing LCD screens with improved back-lighting, provided by colloidal QDs. The color conversion back-lighting provides a larger range of possible colors than the standard phosphor coatings used for color conversion from the LED back-light, making the LCD screens as powerful as the old vacuum-tube electron ray TV sets. Even though this innovative product was technically ready for the market, it was offered for sale only for a period of a few months in 2013, indicating harsh competition with other technologies and, eventually, restricted market penetration in Europe related to the presence of cadmium in the QDs. Another promising optoelectronic application is the implementation of infraredactive QDs onto CMOS-based readout electronics to obtain highly integrated infrared imagers and cameras, operated at wavelengths not accessible for Si-based devices.520 Also, the incorporation of QDs in place of organic dye molecules in conventional OLEDs521 is being actively pursued as a technology with the potential for fast commercialization, owing to extensive developments in hole- and electrontransporting and injecting layers for OLEDs. Exciting progress with respect to NC applications has been obtained in the wide field of biomedicine and especially in theranostics. We have discussed NP-based approaches here, highlighting their advantages in comparison to traditional medications in cancer treatments;mouse models with increased survival rates are encouraging results.480 Similarly successful was the demonstration of gold NPs in cancer-cell-specific, on-demand intracellular amplification of chemoradiation therapy,

Understanding the mechanisms of NC synthesis supports the community's ability to design NC materials with controlled size, shape, and composition. Promising and substantially lesstoxic replacements of the currently favored Cd- or Pb-containing compounds include not only ionically bound compound semiconductors but also covalently bound group IV NPs. The latter (silicon, diamond, silicon carbide, and germanium NPs) benefit from their fluorescence, observed over wide spectral regions covering the near-infrared, visible, and near-ultraviolet ranges and are thus favored for in vivo and in vitro biomedical experiments.514 Also, “carbon dots” exhibit color-tunable emission properties, which are excitation-dependent in this case, making these nanomaterials promising for applications predominantly in the fields of bioimaging, cancer therapy, printing inks, photocatalysis, and optoelectronic devices.515,516 When it comes to real-world applications, the NC research community will soon face significant challenges in commercially competitive areas such as photovoltaics. The power conversion efficiencies of QD-based solar cells have advanced from sub-1% levels in 2005 to over 8.5% in 20132014.436,491,517,518 However, this breakthrough is now challenged by the discovery of highly efficient photovoltaics in lead halide perovskites with power conversion efficiencies approaching 20%, yet with even simpler fabrication procedures than the synthesis and processing of QDs.519 A common problem of both technologies is chemical instability, which limits long-term operation required for VOL. 9

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enabled by their low-cost, lowtemperature, and large-area integration and compatibility with flexible and nonplanar substrates.350,351,501 Novel NMR techniques such as dynamic nuclear polarizationsurface-enhanced NMR spectroscopy will facilitate acquisition of well-resolved spectra from surfacebound organic or inorganic capping ligands and outermost NC atomic layers.502 Understanding the mechanisms of NC synthesis supports the community's ability to design NC materials with controlled size, shape, and composition. Concerning the synthesis of NCs, a particularly difficult task remains: the in situ observation of NC formation at the nucleation stage and at the very early stage of growth. Despite the great potential of in situ XRD, an inherent limitation is the mass transport during the mixing of reagents. We believe that this task may be facilitated by the deployment of microfluidic methods,503506 combined with online monitoring by optical absorption and emission spectroscopy and with in situ structural characterization by synchrotron XRD. Furthermore, microfluidics may enable fast screening of reaction conditions and more repeatable synthesis outputs than in conventional batch syntheses performed in reaction flasks. Some of the key principles of colloidal synthesis of inorganic NCs, such as the use of surfactants, also enter other fields of material developments, including colloidal graphene nanoribbons507 and the synthesis of organic pigment NCs, as discussed above.174 A frequently debated issue in the field of nanomaterials is the question of toxicity508512 and environmental friendliness. The use of the most promising QD materials; those exhibiting record photoluminescence quantum yields,35 record charge transport properties,513 or long photoluminescence wavelengths424;might be restricted by legislation because of the toxicity of their constituents (Pb, Cd, Hg).511

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by energy filtering through the quantum-confined states of NCs.528 Such basic research will certainly continue to lead to novel concepts for devices and applications in the coming years.

the original driving forces for the development of NC research. While this field had stagnated somewhat over the last 20 years, there have been significant advances in understanding photocatalytic processes required for the conversion of solar energy into fuels. In particular, Nidecorated CdS nanorods have been shown to generate H2 (with ethanol as a sacrificial agent) photocatalytically with an external quantum efficiency of above 50%, which is an unprecedented value for chalcogenide NCs with non-noble cocatalysts under visible light.524 This high value was suggested to be achieved through a two-step mechanism of hole transfer via a redox couple • OH/OH at high pH, operating as a highly mobile molecular shuttle between the NC surface and the hole scavenger (ethanol). Prior to applied considerations, NC research is often (if not primarily) dominated by pure curiosity and always has the potential to provide surprising fundamental discoveries. Questions such as to what extent energetic interactions are responsible for the NC self-assembly into more- or less-ordered structures525 are being debated and explored. Superstructures of increasing complexity and/or beauty will be assembled, independent of their impact on device performance. Also, NPs with more elaborate shapes and specific properties will be developed by direct synthesis or with the assistance of galvanic- or cation-exchange reactions.526 Hybrid superlattices of NCs with large inorganic (atomically defined) molecules such as polyoxometallates will bridge the gap between atomically precise and colloidal crystals.527 The increased availability of in situ characterization tools will deliver deeper insights into the formation mechanisms of NCs, their seeds, their shape evolution, and the dynamics of their growth for increased numbers of materials. Nanocrystals will continue to provide a playground to make the unimaginable come closer, such as cold electron transport at room temperature VOL. 9

Conflict of Interest: The authors declare no competing financial interest. Acknowledgment. This article was inspired by the discussions and presentations at the NaNaX6 conference held in Bad-Hofgastein, Austria, May 18-23, 2014. M.K. acknowledges partial financial support by the European Union (EU) via ERC Starting Grant 2012 (Project NANOSOLID, GA No. 306733). L.M. acknowledges partial financial support by the EU via ERC Consolidator Grant 2013 (Project TRANS-NANO, GA No. 614897) and CNECT-ICT-604391 (Graphene Flagship). Z.H. acknowledges Ghent University (GOA Detavernier-Hens), the FWOVlaanderen (G.0760.12), SIM (SIBO SoPPoM), BelSPo (IAP 7.35, photonics@be) and EHH2020 (ETN Phonsi) for research funding. B.A.K. acknowledges financial support from the Robert A. Welch Foundation (F-1464) and the NSF (CHE-1308813). A.C. acknowledges financial support from the EU FP7 under project UNION (FP7-NMP 310250). A.L.R. acknowledges financial support from the Guandong Province Technology Council, China (Project R-IND4601). W.H. thanks the “Gesellschaft für Mikro- und Nanoelektronik (GMe)”, the Austrian Science fund FWF, for financial support via the SFB project IR_ON and acknowledges the use of the services and facilities of the “Energie Campus Nürnberg” and financial support through the “Aufbruch Bayern” initiative of the state of Bavaria. P.R. acknowledges financial support from French National Research Agency (NANOFRET, Grant No. ANR-12-NANO-0007; NIRA, Grant No. ANR-13-BS08-0011). V.I.K. acknowledges financial support from the Center for Advanced Solar Photophysics (CASP), an Energy Frontier Research Center of the U.S. Department of Energy (DOE), Office of Science (OS) and Office of Basic Energy Sciences (OBES). W.J.P. acknowledges funding for the EU (project FutureNanoNeeds). C.R.K. and C.B.M. acknowledge financial support from the U.S. Department of Energy Office of Basic Energy Sciences, Division of Materials Science and Engineering (Award No. DE-SC0002158). D.V.T. and P.G.-S. acknowledge financial support from the NSF MRSEC Program under Award No. DMR 08-20054.

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obtained by laser-induced mechanical impact.522 With a laser pulse, the gold NPs provide a plasmonic nanobubble, a mechanical explosion that destroys the host cancer cell or ejects drugs into the cytoplasm. The same NPs locally enhance external X-rays, leading to a “quadrapeutic” effect, which improves the efficacy of standard chemoradiation therapy by a factor of 101000. Thus, theranostic NPs have the potential to become powerful tools in cancer treatment, as indicated in studies on animals (mice). While there are no doubts that research in these directions will provide a multitude of further treatment routes to heal a wide range of diseases, challenges remain in the transfer of these developments to applications for humans, which includes finding appropriate dosages, ruling out pharmacological interactions, studying side effects and innocuousness, licensing novel NP medicines, and gaining regulatory approval. Less critical, and therefore much more straightforward for clinical use, might be medical applications for which the NPs are applied outside of the body. An example of such promising applications is an extracorporeal blood-cleansing device for sepsis therapy, presented recently by Kang et al.523 In this device, magnetic NPs are used, coated with an engineered human protein, which captures a broad range of pathogens and toxins. Magnets are then used to pull out the toxins and pathogens bound to the magnetic NPs in the blood, which is then returned back to the patient after cleansing. The extracorporeal device is called “biospleen”, and it removes multiple-gram doses of bacteria, fungi, and endotoxins from human blood at a flow rate of 1.25 L per h in vitro. Thus, it represents a dialysis-like blood cleansing system, which could also be applied in parallel with targeted antibiotic therapy to heal diseases and to prolong life. As mentioned in the introduction, photoelectrochemistry was one of

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