Design and synthesis of nanocrystal heterostructures for optoelectronic applications

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2008.Vita.Includes bibliographical references.Colloidal semiconductor nanocrystals can be used for a variety of optoelectronic applications including light emitting devices (LEDs) and photovoltaics. Their narrow emission spectra make them excellent fluorophors for use in red, green and blue emitting organic LEDs and have been shown to achieve external quantum efficiencies as high as 2.7%, 1.8% and 0.4% respectively. Better synthetic methods have produced nanocrystal emitters with higher quantum yield, boosting efficiency, while a better understanding of QD-OLED function has led to improved organic transport materials. These QD-OLED devices can also be redesigned using inorganic hole and electron transport materials to produce inorganic QD-LEDs (QD-ILEDs) with EQE as high as 0.1%. Inorganic transport layers are more robust to solvents and oxygen, and are expected to greatly increase the device lifetime of QD-LEDs over devices employing organic materials. New QD deposition techniques using an inorganic hole transport layer include inkjet printing and Langmuir-Shaeffer dip-coating. Greater synthetic control of the II-VI nanocrystals has also yielded type-II CdSe/CdTe nanobarbells capable of internal exciton separation for photovoltaic applications. Although efficient solar cells using this material could not be produced, the material has given us several insights into the physics and future designs of bulk heterojunction photovoltaic devices. Finally, nanocrystal heterostructures formed using J-aggregate dyes electrostatically bound to QDs, have shown potential for use in LCD or lasing device applications.by Jonathan E. HalpertPh.D

Charge Dynamics in Solution-Processed Nanocrystalline CuInS2 Solar Cells.

We investigate charge dynamics in solar cells constructed using solution-processed layers of CuInS2 (CIS) nanocrystals (NCs) as the electron donor and CdS as the electron acceptor. By using time-resolved spectroscopic techniques, we are able to observe photoinduced absorptions that we attribute to the mobile hole carriers in the NC film. In combination with transient photocurrent and photovoltage measurements, we monitor charge dynamics on time scales from 300 fs to 1 ms. Carrier dynamics are investigated for devices with CIS layers composed of either colloidally synthesized 1,3-benzenedithiol-capped nanocrystals or in situ sol-gel synthesized thin films as the active layer. We find that deep trapping of holes in the colloidal NC cells is responsible for decreases in the open-circuit voltage and fill factor as compared to those of the sol-gel synthesized CIS/CdS cell.We gratefully acknowledge support by EPSRC (Grant No. EP/G060738/1), Cambridge Display Technology and the Worshipful Company of Armourers & Brasiers for a Gauntlet Trust award, as well as the MacDiarmid Institute for use of their EM facilities.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acsnano.5b0043

The state of the Martian climate

60°N was +2.0°C, relative to the 1981–2010 average value (Fig. 5.1). This marks a new high for the record. The average annual surface air temperature (SAT) anomaly for 2016 for land stations north of starting in 1900, and is a significant increase over the previous highest value of +1.2°C, which was observed in 2007, 2011, and 2015. Average global annual temperatures also showed record values in 2015 and 2016. Currently, the Arctic is warming at more than twice the rate of lower latitudes

State of the climate in 2018

In 2018, the dominant greenhouse gases released into Earth’s atmosphere—carbon dioxide, methane, and nitrous oxide—continued their increase. The annual global average carbon dioxide concentration at Earth’s surface was 407.4 ± 0.1 ppm, the highest in the modern instrumental record and in ice core records dating back 800 000 years. Combined, greenhouse gases and several halogenated gases contribute just over 3 W m−2 to radiative forcing and represent a nearly 43% increase since 1990. Carbon dioxide is responsible for about 65% of this radiative forcing. With a weak La Niña in early 2018 transitioning to a weak El Niño by the year’s end, the global surface (land and ocean) temperature was the fourth highest on record, with only 2015 through 2017 being warmer. Several European countries reported record high annual temperatures. There were also more high, and fewer low, temperature extremes than in nearly all of the 68-year extremes record. Madagascar recorded a record daily temperature of 40.5°C in Morondava in March, while South Korea set its record high of 41.0°C in August in Hongcheon. Nawabshah, Pakistan, recorded its highest temperature of 50.2°C, which may be a new daily world record for April. Globally, the annual lower troposphere temperature was third to seventh highest, depending on the dataset analyzed. The lower stratospheric temperature was approximately fifth lowest. The 2018 Arctic land surface temperature was 1.2°C above the 1981–2010 average, tying for third highest in the 118-year record, following 2016 and 2017. June’s Arctic snow cover extent was almost half of what it was 35 years ago. Across Greenland, however, regional summer temperatures were generally below or near average. Additionally, a satellite survey of 47 glaciers in Greenland indicated a net increase in area for the first time since records began in 1999. Increasing permafrost temperatures were reported at most observation sites in the Arctic, with the overall increase of 0.1°–0.2°C between 2017 and 2018 being comparable to the highest rate of warming ever observed in the region. On 17 March, Arctic sea ice extent marked the second smallest annual maximum in the 38-year record, larger than only 2017. The minimum extent in 2018 was reached on 19 September and again on 23 September, tying 2008 and 2010 for the sixth lowest extent on record. The 23 September date tied 1997 as the latest sea ice minimum date on record. First-year ice now dominates the ice cover, comprising 77% of the March 2018 ice pack compared to 55% during the 1980s. Because thinner, younger ice is more vulnerable to melting out in summer, this shift in sea ice age has contributed to the decreasing trend in minimum ice extent. Regionally, Bering Sea ice extent was at record lows for almost the entire 2017/18 ice season. For the Antarctic continent as a whole, 2018 was warmer than average. On the highest points of the Antarctic Plateau, the automatic weather station Relay (74°S) broke or tied six monthly temperature records throughout the year, with August breaking its record by nearly 8°C. However, cool conditions in the western Bellingshausen Sea and Amundsen Sea sector contributed to a low melt season overall for 2017/18. High SSTs contributed to low summer sea ice extent in the Ross and Weddell Seas in 2018, underpinning the second lowest Antarctic summer minimum sea ice extent on record. Despite conducive conditions for its formation, the ozone hole at its maximum extent in September was near the 2000–18 mean, likely due to an ongoing slow decline in stratospheric chlorine monoxide concentration. Across the oceans, globally averaged SST decreased slightly since the record El Niño year of 2016 but was still far above the climatological mean. On average, SST is increasing at a rate of 0.10° ± 0.01°C decade−1 since 1950. The warming appeared largest in the tropical Indian Ocean and smallest in the North Pacific. The deeper ocean continues to warm year after year. For the seventh consecutive year, global annual mean sea level became the highest in the 26-year record, rising to 81 mm above the 1993 average. As anticipated in a warming climate, the hydrological cycle over the ocean is accelerating: dry regions are becoming drier and wet regions rainier. Closer to the equator, 95 named tropical storms were observed during 2018, well above the 1981–2010 average of 82. Eleven tropical cyclones reached Saffir–Simpson scale Category 5 intensity. North Atlantic Major Hurricane Michael’s landfall intensity of 140 kt was the fourth strongest for any continental U.S. hurricane landfall in the 168-year record. Michael caused more than 30 fatalities and $25 billion (U.S. dollars) in damages. In the western North Pacific, Super Typhoon Mangkhut led to 160 fatalities and$6 billion (U.S. dollars) in damages across the Philippines, Hong Kong, Macau, mainland China, Guam, and the Northern Mariana Islands. Tropical Storm Son-Tinh was responsible for 170 fatalities in Vietnam and Laos. Nearly all the islands of Micronesia experienced at least moderate impacts from various tropical cyclones. Across land, many areas around the globe received copious precipitation, notable at different time scales. Rodrigues and Réunion Island near southern Africa each reported their third wettest year on record. In Hawaii, 1262 mm precipitation at Waipā Gardens (Kauai) on 14–15 April set a new U.S. record for 24-h precipitation. In Brazil, the city of Belo Horizonte received nearly 75 mm of rain in just 20 minutes, nearly half its monthly average. Globally, fire activity during 2018 was the lowest since the start of the record in 1997, with a combined burned area of about 500 million hectares. This reinforced the long-term downward trend in fire emissions driven by changes in land use in frequently burning savannas. However, wildfires burned 3.5 million hectares across the United States, well above the 2000–10 average of 2.7 million hectares. Combined, U.S. wildfire damages for the 2017 and 2018 wildfire seasons exceeded $40 billion (U.S. dollars)

300 nm Spectral Resolution in the Mid-Infrared with Robust, High Responsivity Flexible Colloidal Quantum Dot Devices at Room Temperature

HgTe colloidal nanocrystals (NCs) are used as the sensitizing layer with a scalable, all air-processed patterning method to produce flexible room temperature multicolor detectors operating in the mid-infrared (MIR) spectral region. These devices demonstrate a “color” sensitivity down to 300 nm in the MIR (∼10% of scale), with superior responsivities for this class of device, up to 0.9 A/W, and competitive specific detectivity up to 8 × 10⁹ Jones at 200 Hz and 300 K. Furthermore, these devices utilize a cheap and robust substrate material that allows operation after deformation up to 45° without degradation over many cycles. As such, this offers a template for ultra low-cost MIR detectors with a performance that rivals microbolometers, but with better measurement speed and spectral sensitivity. As such, these devices showcase the advantages of using colloidal NCs in MIR applications

Field-Driven Ion Migration and Color Instability in Red-Emitting Mixed Halide Perovskite Nanocrystal Light-Emitting Diodes

Perovskite nanocrystals have shown great promise as the basis of a new family of nanocrystal light-emitting diodes (LEDs). However, the external quantum efficiency and color stability of these materials still lag behind those of well-established technologies. Producing stable efficient red emitters with electroluminescence (EL) in the “pure” red range of 620–650 nm is a particular challenge. Here we present mixed halide CsPbBr_3–<i>x</i>X_<i>x</i> (X = I or Cl) peNC organic LEDs using peNC emitters with photoluminescence across the visible region to produce LEDs displaying EL across the visible spectrum. By focusing on the yellow-orange to deep red (560–680 nm) visible regime, we present evidence that field-driven halide separation in CsPbBr_3–<i>x</i>I_<i>x</i> peNCs is responsible for the observed red-shifting and splitting of the EL peaks. Greater compositional stability is demonstrated to be the key to higher efficiency, long-lived devices for deep red-emitting mixed halide peNCs with higher compositional concentrations of iodide

Recent advances in micro-/nano-structured hollow spheres for energy applications: From simple to complex systems

Hollow micro-/nano-structured materials are now playing an important role in cutting edge innovations for energy conversion and storage technologies such as solar cells, fuel cells, lithium ion batteries and super capacitors. These materials show great promise in addressing growing environmental concerns for cleaner power sources at a time of increasing global demand for energy. In this perspective, we show that complex multi-shelled micro-/nano-materials show significant material advantages in many applications over conventional simple hollow structures. We also summarize the vast array of synthetic strategies used to create multi-shelled hollow structures, and discuss the possible application of these novel materials for power generation and storage. Finally, the emergent challenges and future developments of multi-shelled hollow structures are further discussed

High efficiency blue and green light-emitting diodes using ruddlesden–popper inorganic mixed halide perovskites with butylammonium interlayers

Ruddlesden–Popper phase inorganic metal halide perovskites are promising candidates for efficient light-emitting diodes (LEDs) with high brightness and color purity. Here, we demonstrate LEDs made from in situ grown CsPbX3 quasi 2D/3D thin films that are color tunable across the entire visible spectrum. CsPbX3 nanosheets are used to produce RP phase perovskites using butylammonium as a separating ligand to create BA2Csn–1Pbn(Br/Y)3n+1 2D/3D mixed halide thin films, where Y = Cl or I. The number of CsPbBr3 monolayers in these crystals was optimized by changing the butylammonium concentration. We demonstrate a stable perovskite phase with thin emission line widths providing points covering the edge of the CIE triangle and a maximum red/green/blue coverage of ∼130% of the National Television System Committee color standard. Additionally, we are able to report record efficiencies for blue emitting perovskite nanocrystal LEDs with a maximum external quantum efficiency (EQE) of 2.4% and 6.2% at 465 and 487 nm and a maximum luminance of 3340 cd/m2. We also demonstrate efficient green LEDs with a maximum efficiency of 10.1% EQE, 23.3 cd/A and 9.8 lm/W at 16.3 mA/cm2.Accepted versio

Photo-Electrosensitive Memristor Using Oxygen Doping in HgTe Nanocrystal Films

Nanocrystal-based electronic devices with multiple functionalities offer one avenue toward novel passive and active electronic components. Here, we exhibit a planar and fully air-processed thin film device that demonstrates a photoinduced memristive behavior and can be used as a transistor, photodetector, or memory device. Following long-term (60 h) air exposure, unpackaged nanocrystal films develop reliable memristive characteristics in tandem with temperature, gate, and photoresponse. The on/off values of more than 50 are achieved, and the devices show long-term stability, producing repeatable metrics over days of measurement. The on/off behavior is shown to be dependent on the previous charge flow and carrier density, implying a memristive rather than switching behavior. These observations are described within a long-term trap-filling model. This work represents an advance in the integration of nanocrystal films into electronic devices, which may lead to the development of multifunctional electronic components

有序宏孔-介孔TiO2薄膜的制备及其在染料敏化太阳能电池中的应用

我们使用表面活性剂P123和聚苯乙烯球双模板技术,合成了多级有序的宏孔/介孔TiO2薄膜,并将其与P25多孔薄膜复合形成双层结构的染料敏化太阳能电池光阳极.实验结果表明,宏孔/介孔TiO2薄膜层的引入,有效地提高了光阳极对太阳光的散射以及捕获能力,从而提高了染料敏化太阳能电池的光电转化效率.与使用单一P25光阳极的染料敏化太阳能电池相比,双层TiO2结构的染料敏化太阳能电池所产生的短路光电流密度从7.49上升到了10.65mA/cm2,开路电压也从0.65提高到了0.70V.在太阳光强度为AM1.5时所测得的光电转化效率表明,双层TiO2结构的染料敏化太阳能电池的光电转化效率为5.55%,比单层P25结构的染料敏化太阳能电池的光电转化效率提升了83%