Nicolaas J. Kramer

Controlled Doping of Silicon Nanocrystals Investigated by Solution-Processed Field Effect Transistors

The doping of semiconductor nanocrystals (NCs), which is vital for the optimization of NC-based devices, remains a significant challenge. While gas-phase plasma approaches have been successful in incorporating dopant atoms into NCs, little is known about their electronic activation. Here, we investigate the electronic properties of doped silicon NC thin films cast from solution by field effect transistor analysis. We find that, analogous to bulk silicon, boron and phosphorus electronically dope Si NC thin films; however, the dopant activation efficiency is only ∼10(-2)-10(-4). We also show that surface doping of Si NCs is an effective way to alter the carrier concentrations in Si NC films.

Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus

Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicons low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year.

Metal-insulator transition in films of doped semiconductor nanocrystals

To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition.

Nonequilibrium-Plasma-Synthesized ZnO Nanocrystals with Plasmon Resonance Tunable via Al Doping and Quantum Confinement

Metal oxide semiconductor nanocrystals (NCs) exhibit localized surface plasmon resonances (LSPRs) tunable within the infrared (IR) region of the electromagnetic spectrum by vacancy or impurity doping. Although a variety of these NCs have been produced using colloidal synthesis methods, incorporation and activation of dopants in the liquid phase has often been challenging. Herein, using Al-doped ZnO (AZO) NCs as an example, we demonstrate the potential of nonthermal plasma synthesis as an alternative strategy for the production of doped metal oxide NCs. Exploiting unique, thoroughly nonequilibrium synthesis conditions, we obtain NCs in which dopants are not segregated to the NC surfaces and local doping levels are high near the NC centers. Thus, we achieve overall doping levels as high as 2 × 10(20) cm(-3) in NCs with diameters ranging from 12.6 to 3.6 nm, and for the first time experimentally demonstrate a clear quantum confinement blue shift of the LSPR energy in vacancy- and impurity-doped semiconductor NCs. We propose that doping of central cores and heavy doping of small NCs are achievable via nonthermal plasma synthesis, because chemical potential differences between dopant and host atoms-which hinder dopant incorporation in colloidal synthesis-are irrelevant when NC nucleation and growth proceed via irreversible interactions among highly reactive gas-phase ions and radicals and ligand-free NC surfaces. We explore how the distinctive nucleation and growth kinetics occurring in the plasma influences dopant distribution and activation, defect structure, and impurity phase formation.

Requirements for plasma synthesis of nanocrystals at atmospheric pressures

While well-defined high quality semiconductor nanocrystals have been synthesized successfully in low pressure nonthermal plasmas, moving the field of plasma nanoparticle synthesis to atmospheric pressures is important for lowering its cost and making the process attractive for some industrial applications. Here we present a heating and charging model for silicon nanoparticles during their synthesis in plasmas maintained over a wide range of pressures (10 − 105 Pa). We consider three collisionality regimes and determine the dominant contribution of each regime to heating and charging of nanoparticles under various plasma conditions. For plasmas maintained at atmospheric pressures we find that the ion current is mainly due to the collisional hydrodynamic contribution. Based on the model, we predict that the formation of nanocrystals at atmospheric pressure requires significantly higher plasma densities than those at low pressures. Strong nanoparticle cooling at atmospheric pressures necessitates high ion densities to reach temperatures required for crystallization of nanoparticles. Using experimentally determined plasma properties from the literature we estimate the nanoparticle temperature that can be achieved during synthesis at atmospheric pressures and predict that temperatures well above those required for crystallization can be achieved. Based on these results we suggest design principles for nanocrystal synthesis at atmospheric pressures.

Environmental photostability of SF6-etched silicon nanocrystals

We report on the long-term environmental stability of the photoluminescent (PL) properties of silicon nanocrystals (SiNCs). We prepared sulfur hexafluoride (SF(6)) etched SiNCs in a two-stage plasma reactor and investigated their PL stability against UV irradiation in air. Unlike SiNCs with hydrogen-passivated surfaces, the SF(6)-etched SiNCs exhibit no photobleaching upon extended UV irradiation despite surface oxidation. Furthermore, the PL quantum yield also remains stable upon heating the SF(6)-etched SiNCs up to 160 °C. The observed thermal and UV stability of SF(6)-etched SiNCs combined with their PL quantum yields of up to ~50% make them attractive candidates for UV downshifting to enhance the efficiency of solar cells. Electron paramagnetic spin resonance indicates that the SF(6)-etched SiNCs have a lowered density of defect states, both as-formed and after room temperature oxidation in air.

Controlled synthesis of germanium nanoparticles by nonthermal plasmas

The size, composition, and crystallinity of plasma produced nanoparticles are crucial factors for their physical and chemical properties. Here, we investigate the role of the process gas composition, particularly the hydrogen (H2) flow rate, on germanium (Ge) nanoparticles synthesized from a chlorinated precursor by nonthermal plasma. We demonstrate that the gas composition can significantly change the nanoparticle size and also adjust the surface chemistry by altering the dominant reaction mechanisms. A red shift of the Ge-Clx infrared absorptions with increasing H2 flow indicates a weakening of the Ge-Clx bonds at high H2 content. Furthermore, by changing the gas composition, the nanoparticles microstructure can be controlled from mostly amorphous at high hydrogen flow to diamond cubic crystalline at low hydrogen flow.