Name: inkjet printing all inorganic halide perovskite inks for photovoltaic applications
Uploaded: 2019-01-22T14:20:00
Description: Watch this Scientific Journal Video about Inkjet Printing All Inorganic Halide Perovskite Inks for Photovoltaic Applications at JoVE.com

This work was supported by the National Science Foundation, through the Nebraska MRSEC (Grant DMR-1420645), CHE-1565692, and CHE-145533 as well as the Nebraska Center for Energy Science Research.

CAUTION: Please consult the lab&#8217;s material safety data sheets (MSDS) before proceeding. The chemicals used in these synthesis protocols have associated health hazards. Additionally, nanomaterials have additional hazards compared to their bulk counterpart. Please use all appropriate safety practices when performing a nanocrystal reaction including the use of a fume hood or glovebox and the proper personal protective equipment (safety glasses, gloves, lab coat, pants, closed-toe shoes, etc.).
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<ol>
	<li>Weber, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CH3NH3PbX3,+ein+Pb(II)-System+mit+kubischer+Perowskitstruktur+/+CH3NH3PbX3,+a+Pb(II)-System+with+Cubic+Perovskite+Structure.">CH3NH3PbX3, ein Pb(II)-System mit kubischer Perowskitstruktur / CH3NH3PbX3, a Pb(II)-System with Cubic Perovskite Structure.</a> Zeitschrift f&#252;r Naturforschung B. 33, 1443-1445 (1978).</li><li>Weber, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=(+x+=+0-3+),+ein+Sn+(+II+)+-System+mit+kubischer+Perowskitstruktur.">( x = 0-3 ), ein Sn ( II ) -System mit kubischer Perowskitstruktur.</a> Zeitschrift f&#252;r Naturforschung B. 33, 862-865 (1978).</li><li>Kojima, A., Teshima, K., Shirai, Y., Miyasaka, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organometal+Halide+Perovskites+as+Visible-Light+Sensitizers+for+Photovoltaic+Cells.">Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells.</a> Journal of the American Chemical Society. 131, 6050-6051 (2009).</li><li>. National Renewable Energy Laboratory NREL Best Research-Cell Efficiencies Available from: <a target="_blank" href="https://www.nrel.gov/pv/assets/images/efficiency-chart.png">https://www.nrel.gov/pv/assets/images/efficiency-chart.png</a> (2018)</li><li>Chen, Z., Wang, J. J., Ren, Y., Yu, C., Shum, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Schottky+solar+cells+based+on+CsSnI+3+thin-films.">Schottky solar cells based on CsSnI 3 thin-films.</a> Applied Physics Letters. 101 (9), 93901 (2012).</li><li>Sanehira, E. 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C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Crystal+growth+of+the+perovskite+semiconductor+CsPbBr3:+A+new+material+for+high-energy+radiation+detection.">Crystal growth of the perovskite semiconductor CsPbBr3: A new material for high-energy radiation detection.</a> Crystal Growth and Design. 13 (7), 2722-2727 (2013).</li><li>Ilie, C. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Inkjet+printable-photoactive+all+inorganic+perovskite+films+with+long+effective+photocarrier+lifetimes.">Inkjet printable-photoactive all inorganic perovskite films with long effective photocarrier lifetimes.</a> Journal of Physics Condensed Matter. 30 (18), (2018).</li><li>Shoaib, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Directional+Growth+of+Ultralong+CsPbBr3Perovskite+Nanowires+for+High-Performance+Photodetectors.">Directional Growth of Ultralong CsPbBr3Perovskite Nanowires for High-Performance Photodetectors.</a> Journal of the American Chemical Society. 139 (44), 15592-15595 (2017).</li><li>Swarnkar, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantum+dot-induced+phase+stabilization+of+a-CsPbI3+perovskite+for+high-efficiency+photovoltaics.">Quantum dot-induced phase stabilization of a-CsPbI3 perovskite for high-efficiency photovoltaics.</a> Science. 354 (6308), 92-96 (2016).</li><li>Kumar, M. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lead-free+halide+perovskite+solar+cells+with+high+photocurrents+realized+through+vacancy+modulation.">Lead-free halide perovskite solar cells with high photocurrents realized through vacancy modulation.</a> Advanced Materials. 26 (41), 7122-7127 (2014).</li><li>Burschka, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sequential+deposition+as+a+route+to+high-performance+perovskite-sensitized+solar+cells.">Sequential deposition as a route to high-performance perovskite-sensitized solar cells.</a> Nature. 499 (7458), 316-319 (2013).</li><li>Dirin, D. N., Cherniukh, I., Yakunin, S., Shynkarenko, Y., Kovalenko, M. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solution-Grown+CsPbBr+3+Perovskite+Single+Crystals+for+Photon+Detection.">Solution-Grown CsPbBr 3 Perovskite Single Crystals for Photon Detection.</a> Chemistry of Materials. 28 (23), 8470-8474 (2016).</li><li>Zhou, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vapor+Growth+and+Tunable+Lasing+of+Band+Gap+Engineered+Cesium+Lead+Halide+Perovskite+Micro/Nanorods+with+Triangular+Cross+Section.">Vapor Growth and Tunable Lasing of Band Gap Engineered Cesium Lead Halide Perovskite Micro/Nanorods with Triangular Cross Section.</a> ACS Nano. 11 (2), 1189-1195 (2017).</li><li>Teng, K. F., Vest, R. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Application+of+Ink+Jet+Technology+on+Photovoltaic+Metallization.">Application of Ink Jet Technology on Photovoltaic Metallization.</a> IEEE Electron Device Letters. 9 (11), 591-593 (1988).</li><li>Habas, S. E., Platt, H. a. S., van Hest, M. F. A. M., Ginley, D. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Low-Cost+Inorganic+Solar+Cells:+From+Ink+To+Printed+Device.">Low-Cost Inorganic Solar Cells: From Ink To Printed Device.</a> Chemical Reviews. 110 (11), 6571-6594 (2010).</li><li>Leenen, M. A. M., Arning, V., Thiem, H., Steiger, J., Anselmann, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Printable+electronics:+Flexibility+for+the+future.">Printable electronics: Flexibility for the future.</a> Physica Status Solidi (A) Applications and Materials Science. 206 (4), 588-597 (2009).</li><li>Koolyk, M., Amgar, D., Aharon, S., Etgar, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+cesium+lead+halide+perovskite+nanoparticle+growth;+focusing+and+de-focusing+of+size+distribution.">Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution.</a> Nanoscale. 8 (12), 6403-6409 (2016).</li><li>Palazon, F., Di Stasio, F., Lauciello, S., Krahne, R., Prato, M., Manna, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evolution+of+CsPbBr+3+nanocrystals+upon+post-synthesis+annealing+under+an+inert+atmosphere.">Evolution of CsPbBr 3 nanocrystals upon post-synthesis annealing under an inert atmosphere.</a> Journal of Materials Chemistry C. 4 (39), 9179-9182 (2016).</li><li>Scherrer, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bestimmung+der+Gr&#246;&#223;e+und+der+inneren+Struktur+von+Kolloidteilchen+mittels+R&#246;ntgenstrahlen.+Nachrichten+von+der+Gesellschaft+der+Wissenschaften+zu+G&#246;ttingen.">Bestimmung der Gr&#246;&#223;e und der inneren Struktur von Kolloidteilchen mittels R&#246;ntgenstrahlen. Nachrichten von der Gesellschaft der Wissenschaften zu G&#246;ttingen.</a> Nachrichten von der Gesellschaft der Wissenschaften zu G&#246;ttingen, Mathematisch-Physikalische Klasse. 2, 98-100 (1918).</li><li>Shekhirev, M., Goza, J., Teeter, J., Lipatov, A., Sinitiskii, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Cesium+Lead+Halide+Quantum+Dots.">Synthesis of Cesium Lead Halide Quantum Dots.</a> Journal of Chemical Education. 94 (8), 1150-1156 (2017).</li></ol>

There are many parameters involved in the inkjet printing process that affect the final printed film. The discussion of all those parameters is beyond the scope of this protocol, but as this protocol focuses on a solution-based synthesis and deposition method, it is appropriate to give a short comparison to other well-known solution-based deposition methods: the spin-coating method and the doctor-blade method.
The spin-coating method is very fast, produces uniform films, and is low cost. The f...

Dieter Weber synthesized the first organic-inorganic hybrid&#160;halide&#160;perovskites in 19781,2. Roughly 30 years later in 2009, Akihiro Kojima and collaborators fabricated photovoltaic devices using the same organic-inorganic hybrid&#160;halide&#160;perovskites synthesized by Weber, namely, CH3NH3PbI3 and CH3NH3PbBr33. These experiments were the beginning of a subsequent tidal wave of research focusing on the photovoltaic properties of organic-inorganic hybrid halide perovskites. From 2009 to 2018, the device power conversion efficiency dramatically increased from 3.8%3 to over 23%4, making organic-inorganic hybrid&#160;halide perovskites comparable to Si-based solar cells. As with the organic-inorganic halide-based perovskites, the inorganic halide-based perovskites started gaining traction in the research community around 2012 when the first photovoltaic device efficiency was measured to be 0.9%5. Since 2012 the all inorganic halide-based perovskites have come a long way with some device efficiencies measured to be over 13% as in the 2017 study by Sanehira et al.6&#160;Both the organic-based and inorganic-based perovskites find applications related to lasers7,8,9,10, light emitting diodes11,12,13, high energy radiation detection14, photo detection15,16, and of course photovoltaic applications5,15,17,18. Over almost the past decade, many different synthesis techniques have emerged from scientists and engineers ranging from solution processed methods to vacuum vapor deposition techniques19,20,21. The halide&#160;perovskites synthesized using a solution-processed method are advantageous as they can easily be employed as inks for inkjet printing15.
In 1987, the first reported use of inkjet printing of solar cells was presented. Since then, scientists and engineers have sought ways to successfully print all inorganic solar cells with attractive performance properties and low implementation costs22. There are many advantages to inkjet printing solar cells, as compared to some of the common vacuum based fabrication methods. An important aspect of the inkjet printing method is that solution-based materials are used as inks. This opens the door for trials of many different materials, such as inorganic&#160;perovskite-based inks, which can be synthesized by facile wet chemical methods. In other words, inkjet printing of solar cell materials is a low-cost route to rapid prototyping. Inkjet printing also has the advantages of being able to print large areas on flexible substrates and print by design at low temperatures in atmospheric conditions. Furthermore, inkjet printing is highly suitable for mass production allowing for realistic low cost roll-to-roll implementation23,24.
In this article, we first discuss the steps involved with synthesizing inorganic&#160;perovskite quantum dot inks for inkjet printing. Then, we describe the additional steps for preparing inks for printing and the actual procedures for inkjet printing a photoactive film using a commercially available inkjet printer. Finally, we discuss the characterization of the printed films which is necessary to ensure the films are of proper chemical and crystal composition for high quality device performance.

<table>
	<tbody>
		<tr>
			<td>Oleic acid, 90%</td>
			<td>Sigma Aldrich</td>
			<td>364525</td>
			<td>Technical grade</td>
		</tr>
		<tr>
			<td>Oleylamine, 70%</td>
			<td>Sigma Aldrich</td>
			<td>O7805</td>
			<td>Technical grade</td>
		</tr>
		<tr>
			<td>1-octadecene, 90%</td>
			<td>Sigma Aldrich</td>
			<td>O806</td>
			<td>Technical grade</td>
		</tr>
		<tr>
			<td>Acetone, &#62;95%</td>
			<td>Fisher</td>
			<td>67641</td>
			<td>Certified ACS</td>
		</tr>
		<tr>
			<td>Cesium Carbonate, 99%</td>
			<td>Chem-Impex</td>
			<td>1955</td>
			<td>Assay</td>
		</tr>
		<tr>
			<td>Hexane, 98.5%</td>
			<td>Sigma Aldrich</td>
			<td>178918</td>
			<td>Mixture of isomers</td>
		</tr>
		<tr>
			<td>Cyclohexane, 99.9%</td>
			<td>Sigma Aldrich</td>
			<td>110827</td>
			<td></td>
		</tr>
		<tr>
			<td>Lead(II) bromide, 98%</td>
			<td>Sigma Aldrich</td>
			<td>211141</td>
			<td></td>
		</tr>
		<tr>
			<td>Lead(II) iodide, 99%</td>
			<td>Sigma Aldrich</td>
			<td>211168</td>
			<td></td>
		</tr>
	</tbody>
</table>

inkjet printing all inorganic halide perovskite inks for photovoltaic applications

A method for synthesizing photoactive inorganic&#160;perovskite quantum dot inks and an inkjet printer deposition method, using the synthesized inks, are demonstrated. The ink synthesis is based on a simple wet chemical reaction and the inkjet printing protocol is a facile step by step method. The inkjet printed thin films have been characterized by X-ray diffraction, optical absorption spectroscopy, photoluminescent spectroscopy, and electronic transport measurements. X-ray diffraction of the printed quantum dot films indicates a crystal structure consistent with an orthorhombic room temperature phase with (001) orientation. In conjunction with other characterization methods, the X-ray diffraction&#160;measurements show high quality films can be obtained through the inkjet printing method.

Crystal Structure Characterization
Characterizing the crystal structure is vital regarding the synthesis of the inorganic&#160;perovskites. X-ray diffraction (XRD) was performed in air at room temperature on a diffractometer using a 1.54 &#197; wavelength Cu-K&#945; light source. Using the above protocols should lead to a room temperature orthorhombic crystal structure for the CsPbBr3 quantum dot inks as shown...

Watch this Scientific Journal Video about Inkjet Printing All Inorganic Halide Perovskite Inks for Photovoltaic Applications at JoVE.com

Inkjet Printing All Inorganic Halide Perovskite Inks for Photovoltaic Applications

A protocol for synthesizing inorganic-lead-halide hybrid perovskite quantum dot inks for inkjet printing and the protocol for preparing and printing the quantum dot inks in an inkjet printer with post characterization techniques are presented.

A method for synthesizing photoactive inorganic&#160;perovskite quantum dot inks and an inkjet printer deposition method, using the synthesized inks, are ...

The main advantages of this technique are that it is well suited for large area deposition, rapid prototyping and print by design, which suggests high potential for roll-to-roll manufacturing. Though this system can provide insight into inorganic photovoltaics it can also be applied to other systems such as organic photovoltaics or biophysics. Demonstrating the chemical synthesis procedure will be Mason McCormick, an undergraduate from the Sinitsky laboratory.An imprinting procedure will be demonstrated by Dylan Richmond from the Ilie laboratory. To prepare the cesium oleate precursor add 0.203 grams of cesium carbonate 10 milliliters of octadecene and 1.025 milliliters of oleic acid to a three neck round bottom flask containing 2.54 centimeter magnetic stir bar. Place a thermometer into one of the necks of the round bottom flask via a rubber septum.Next, place a rubber septum into one of the remaining necks of the round bottom flask and attach the third neck to the nitrogen gas line via a Schlenk line. Place the mixture under nitrogen atmosphere. Heat the mixture to 150 degrees celsius with constant stirring at a stirring speed of 399 millimeters per second until the cesium carbonate fully dissolves.Following this lower the temperature to 100 degrees celsius to avoid precipitation and decomposition of the cesium oleate and continue stirring at a stirring speed of 399 millimeters per second. To prepare the oleylamine lead bromide precursor add 1.35 millimoles of lead bromide 37.5 milliliters of octadecene 7.5 milliliters of olaylamine and 3.75 milliliters of oleic acid to a three neck round bottom flask containing a magnetic stir bar. Next place a thermometer into one of the necks of the round bottom flask and seal with polymer film.Place a rubber septum in one of the remaining necks of the round bottom flask and attach the third neck to the nitrogen gas line via a Schlenk line. Place mixture under nitrogen atmosphere. Heat the mixture to 100 degrees celsius with constant stirring at a stirring speed of 599 millimeters per second until the lead bromide is fully dissolved.Now, heat the mixture to 170 degrees celsius with constant stirring and observe the color change to dark yellow once the temperature reaches 170 degrees celsius. Continue stirring at 170 degrees celsius. Using a two milliliter glass syringe with a 10 centimeter long 18 gauge needle extract 1.375 milliliters of cesium oleate precursor from the three neck round bottom flask.Quickly inject this precursor into the three neck round bottom flask containing the oleylamine lead bromide precursor. After waiting five seconds remove the three neck round bottom flask from the heat and immerse it in an ice water bath. Separate the solution in the three neck round bottom flask equally into two test tubes.Add 25 milliliters of acetone to each of the supernatant solutions. Next, separate the quantum dots using a centrifuge at 2431.65G for five minutes at room temperature. Now dissolve the separated quantum dots in 10 to 25 milliliters of cyclohexane.To ensure that the inks print in the desired location draw a straight line at the edge of the disk and continue onto the CD disk tray. Place the desired substrate over the ink images printed on the disk and attach it to the disk using an adhesive such as double sided tape. Before filling the ink cartridges ensure the orange cover is installed correctly on the bottom of the ink cartridge to prevent ink from spilling out.Using a pipette inject the prepared quantum dot ink into the top of the ink cartridge. Once the cartridge is filled to the desired amount of ink plug the top with the rubber septum and carefully remove the orange cover. Next place the ink cartridge in the printer head and ensure that is snaps into place.Then insert the remaining cartridges before continuing to the next step. At this point the printer will accept the disk tray and print perovskites on the substrate. After printing is complete check that the inks actually printed onto the substrate as clogging is a common problem.Finally hold a UV lamp over the substrate to check if the printing was successful and a luminescing film is observed. Characterization of the synthesized inorganic perovskites is vital to confirm the crystal structure. The X Ray defraction results indicate that the crystalline cesium lead bromide quantum dot inks prepared using this protocol maintain an orthorhombic room temperature perovskite structure after the ink jet printing process.It is well known that the optical properties of these inorganic perovskite quantum dots are sensitive to quantum dot size and stoichiometry of the inorganic and halide atoms. The photoluminescence profile for cesium lead bromide shows a peak around 520 nanometers and the optical absorption profile shows an excitonic peak around 440 nanometers. Current voltage and capacitance voltage measurements were taken for the printed films under dark and light conditions as shown here.Under illumination the measured kind increased linearly and indicates that the films are photoactive. The films exhibit very low capacitance under dark conditions when no illumination is present. As can be seen here.Under light illumination the zero bias measured capacitance increases and is another indication that the films are photoactive. While attempting this procedure it's important to remember to keep both the printer head and gaskets as clean as possible. This will ultimately dictate successful printing.Following this procedure other methods like probe microscopy and time resolved luminescence can be performed in order to answer additional questions like what is the surface termination and surface morphology, and what are the exciton recombination dynamics. After it's development this technique paved the way for researchers in the fields of chemistry, physics and material science to explore roll-to-roll ready, photovoltaic systems composed of organic and inorganic semi conductor materials and the associated device interfaces. This technique proved to be a great educational tool as it was introduced in the upper level inorganic chemistry laboratory course at the University of Nebraska-Lincoln to introduce students to a variety of important concepts ranging from calyceal synthesis and quantum size affects to photovoltaics and renewable energy.Don't forget that working with lead based products and solvents like hexane, cyclohexane or acetone can be extremely hazardous and precautions such as using proper protective clothing and proper ventilation should always be taken when performing this procedure.

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Chemistry

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials.

Herein the procedures for plasma enhanced chemical vapor deposition of perfluoroalkanes on microporous materials such as metal-organic frameworks to enhance their stability and hydrophobicity are described. Furthermore, breakthrough testing of milligram quantities of samples is described in detail.

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1&#039;,1&#039;&#039;-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a sterically demanding ligand, has increased in recent years. The metastable Sn(I) halide is synthesized at&#160;&#34;outer space conditions&#34; via the preparative co-condensation technique. Thereby, the subhalide is synthesized in an oven at high temperatures, around 1,300 &#176;C, and at reduced pressure by the reaction of elemental tin with hydrogen halide gas (e.g., HCl). The subhalide (e.g., SnCl) is trapped within a matrix of an inert solvent, like toluene at -196 &#176;C. Heating the solid matrix to -78 &#176;C gives a metastable solution of the subhalide. The metastable subhalide solution is highly reactive but can be stored at -78 &#176;C for several weeks. On heating the solution to room temperature, a disproportionation reaction occurs, leading to elemental tin and the corresponding dihalide. By applying bulky ligands like Si(SiMe3)3, the intermediate metalloid cluster compounds can be trapped before complete disproportionation to elemental tin. Hence, the reaction of a metastable Sn(I)Cl solution with Li-Si(SiMe3)3 gives [Sn10(Si(SiMe3)3)4]2- 1 as black crystals in high yield. 1 is formed via a complex reaction sequence including salt metathesis, disproportionation, and degradation of larger clusters. Further, 1 can be analyzed by various methods like NMR or single crystal X-ray structure analysis.

The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique

The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a ...

Insights into the Interactions of Amino Acids and Peptides with Inorganic Materials Using Single-Molecule Force Spectroscopy

The interactions between proteins or peptides and inorganic materials lead to several interesting processes. For example, combining proteins with minerals leads to the formation of composite materials with unique properties. In addition, the undesirable process of biofouling is initiated by the adsorption of biomolecules, mainly proteins, on surfaces. This organic layer is an adhesion layer for bacteria and allows them to interact with the surface. Understanding the fundamental forces that govern the interactions at the organic-inorganic interface is therefore important for many areas of research and could lead to the design of new materials for optical, mechanical and biomedical applications. This paper demonstrates a single-molecule force spectroscopy technique that utilizes an AFM to measure the adhesion force between either peptides or amino acids and well-defined inorganic surfaces. This technique involves a protocol for attaching the biomolecule to the AFM tip through a covalent flexible linker and single-molecule force spectroscopy measurements by atomic force microscope. In addition, an analysis of these measurements is included.

Here we present a protocol to measure the force of interactions between a well-defined inorganic surface and either peptides or amino acids by single-molecule force spectroscopy measurements using an atomic force microscope (AFM). The information obtained from the measurement is important to better understand the peptide-inorganic material interphase.

The interactions between proteins or peptides and inorganic materials lead to several interesting processes. For example, combining proteins with minerals ...

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH3NH3I) and methylammonium bromide (CH3NH3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH3NH3PbX3 with X = I, Br, Cl and their mixture) films with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH3NH3PbI3-xBrx by exposing the substrate to vapors of a mixture of CH3NH3I and CH3NH3Br at reduced pressure and 120 &#176;C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH3NH3PbI3-xBrx with 0&#160;&#8804; x&#160;&#8804; 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV&#160;&#8804; Eg&#160;&#8804; 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH3NH3PbI3-xClx. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.

Here, we present a protocol for the synthesis of CH3NH3I and CH3NH3Br precursors and the subsequent formation of pinhole-free, continuous CH3NH3PbI3-xBrx thin films for the application in high efficiency solar cells and other optoelectronic devices.

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, ...

Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications

The rock material pentlandite with the composition Fe4.5Ni4.5S8 was synthesized via high temperature synthesis from the elements. The structure and composition of the material was characterized via powder X-ray diffraction (PXRD), M&#246;ssbauer spectroscopy (MB), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and energy dispersive X-ray spectroscopy (EDX). Two preparation methods of pentlandite bulk electrodes are presented. In the first approach a piece of synthetic pentlandite rock is directly contacted via a wire ferrule. The second approach utilizes pentlandite pellets, pressed from finely ground powder, which is immobilized in a Teflon casing. Both electrodes, whilst being prepared by an additive-free method, reveal high durability during electrocatalytic conversions in comparison to common drop-coating methods. We herein showcase the striking performance of such electrodes to accomplish the hydrogen evolution reaction (HER) and present a standardized method to evaluate the electrocatalytic performance by electrochemical and gas chromatographic methods. Furthermore, we report stability tests via potentiostatic methods at an overpotential of 0.6 V to explore the material limitations of the electrodes during electrolysis under industrial relevant conditions.

A facile preparation method of electrodes using the bulk material Fe4.5Ni4.5S8 is presented. This method provides an alternative technique to conventional electrode fabrication and describes prerequisites for unconventional electrode materials including a straightforward electrocatalytic testing method.

The rock material pentlandite with the composition Fe4.5Ni4.5S8 was synthesized via high temperature synthesis from the elements. The structure and ...

Stereolithographic 3D Printing with Renewable Acrylates

The accessibility of cost-competitive renewable materials and their application in additive manufacturing is essential for an efficient biobased economy. We demonstrate the rapid prototyping of sustainable resins using a stereolithographic 3D printer. Resin formulation takes place by straightforward mixing of biobased acrylate monomers and oligomers with a photoinitiatior and optical absorber. Resin viscosity is controlled by the monomer to oligomer ratio and is determined as a function of shear rate by a rheometer with parallel plate geometry. A stereolithographic apparatus charged with the biobased resins is employed to produce complex shaped prototypes with high accuracy. The products require a post-treatment, including alcohol rinsing and UV irradiation, to ensure complete curing. The high feature resolution and excellent surface finishing of the prototypes is revealed by scanning electron microscopy.

A protocol for additive manufacturing with renewable photopolymer resins on a stereolithography apparatus is presented.

The accessibility of cost-competitive renewable materials and their application in additive manufacturing is essential for an efficient biobased economy. ...

Solution-Processed "Silver-Bismuth-Iodine" Ternary Thin Films for Lead-Free Photovoltaic Absorbers

Bismuth-based hybrid perovskites are regarded as promising photo-active semiconductors for environment-friendly and air-stable solar cell applications. However, poor surface morphologies and relatively high bandgap energies have limited their potential. Silver-bismuth-iodine (Ag-Bi-I) is a promising semiconductor for optoelectronic devices. Therefore, we demonstrate the fabrication of Ag-Bi-I ternary thin films using material solution processing. The resulting thin films exhibit controlled surface morphologies and optical bandgaps according to their thermal annealing temperatures. In addition, it has been reported that Ag-Bi-I ternary systems crystallize to AgBi2I7, Ag2BiI5, etc. according to the ratio of the precursor chemicals. The solution-processed AgBi2I7 thin films exhibit a cubic-phase crystal structure, dense, pinhole-free surface morphologies with grains ranging in size from 200 to 800 nm, and an indirect bandgap of 1.87 eV. The resultant AgBi2I7 thin films show good air stability and energy band diagrams, as well as surface morphologies and optical bandgaps suitable for lead-free and air-stable single-junction solar cells. Very recently, a solar cell with 4.3% power conversion efficiency was obtained by optimizing the Ag-Bi-I crystal compositions and solar cell device architectures.

Solution-Processed &quot;Silver-Bismuth-Iodine&quot; Ternary Thin Films for Lead-Free Photovoltaic Absorbers

Herein, we present detailed protocols for solution-processed silver-bismuth-iodine (Ag-Bi-I) ternary semiconductor thin films fabricated on TiO2-coated transparent electrodes and their potential application as air-stable and lead-free optoelectronic devices.

Bismuth-based hybrid perovskites are regarded as promising photo-active semiconductors for environment-friendly and air-stable solar cell applications. ...

Reactive Inkjet Printing and Propulsion Analysis of Silk-based Self-propelled Micro-stirrers

In this study, a protocol for using reactive inkjet printing to fabricate enzymatically propelled silk swimmers with well-defined shapes is reported. The resulting devices are an example of self-propelled objects capable of generating motion without external actuation and have potential applications in medicine and environmental sciences for a variety of purposes ranging from micro-stirring, targeted therapeutic delivery, to water remediation (e.g., cleaning oil spills). This method employs reactive inkjet printing to generate well-defined small-scale solid silk structures by converting water soluble regenerated silk fibroin (silk I) to insoluble silk fibroin (silk II). These structures are also selectively doped in specific regions with the enzyme catalase in order to produce motion via bubble generation and detachment. The number of layers printed determines the three-dimensional (3D) structure of the device, and so here the effect of this parameter on the propulsive trajectories is reported. The results demonstrate the ability to tune the motion by varying the dimensions of the printed structures.

This protocol demonstrates the ability to utilize reactive inkjet printing to print self-motile biocompatible and environmentally friendly micro-stirrers for use in biomedical and environmental applications.

In this study, a protocol for using reactive inkjet printing to fabricate enzymatically propelled silk swimmers with well-defined shapes is reported. The ...