This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES) under award number DE-SC0019345. Seung Kyun Ha was partially supported by the Kwanjeong Education Foundation Overseas Doctoral Program Scholarship. This work made use of the MRSEC Shared Experimental Facilities at MIT, supported by the National Science Foundation under award number DMR-08-19762. We thank Eric Powers for assistance with proofing and editing.

NOTE: Simpler notations of &#8216;n = 1 BX&#8217; and &#8216;n = 2 ABX&#8217; will be used from here instead of the complex chemical formula of L2BX4 and L2[ABX3]BX4, respectively. For better stability and optical properties of resulting perovskite nanoplatelets, it is recommended to complete the whole procedure under inert conditions49 (i.e., a nitrogen glovebox).
1. Preparation of perovskite nanopl...

The product of this synthesis is colloidal lead halide nanoplatelets capped by alkylammonium halide surface ligands (Figure 1a). Figure 1b demonstrates the synthetic procedure of colloidal perovskite nanoplatelets via ligand-assisted reprecipitation. To summarize, constituent precursor salts were dissolved in a polar solvent DMF in specific ratios for desired thickness and composition, and then injected into toluene, which is nonpolar. Due to the abrupt change i...

In the past decade, fabrication of lead halide perovskites solar cells1,2,3,4,5,6 has effectively highlighted the excellent properties of this semiconductor material, including long carrier diffusion lengths7,8,9,10, compositional tunability4,5,11 and low-cost synthesis12. In particular, the unique nature of defect tolerance13,14 makes lead halide perovskites fundamentally different from other semiconductors and thus highly promising for next-generation optoelectronic applications.
In addition to solar cells, lead halide perovskites have been shown to make excellent optoelectronic devices such as light-emitting diodes6,15,16,17,18,19,20,21,22, lasers23,24,25, and photodetectors26,27,28. Especially, when prepared in the form of colloidal nanocrystals18,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43, lead halide perovskites may exhibit strong quantum- and dielectric-confinement, large exciton binding energy44,45, and bright luminescence17,19 along with facile solution processability. Various reported geometries including quantum dots29,30,31,32, nanorods33,34 and nanoplatelets18,35,36,37,38,39,40,41,43 further demonstrate the shape tunability of lead halide perovskite nanocrystals.
Among those nanocrystals, colloidal two-dimensional (2D) lead halide perovskites, or &#8220;perovskite nanoplatelets&#8221;, are especially promising for light-emitting applications due to strong confinement of charge carriers, large exciton binding energy reaching up to hundreds of meV44, and spectrally narrow emission from thickness-pure ensembles of nanoplatelets39. Additionally, anisotropic emission reported for 2D perovskite nanocrystals46 and other 2D semiconductors47,48 highlights the potential of maximizing outcoupling efficiency from perovskite nanoplatelet-based light-emitting devices.
Here, we demonstrate a protocol for the simple, universal, room-temperature synthesis of colloidal lead halide perovskite nanoplatelets via a ligand-assisted reprecipitation technique36,38,49. Perovskite nanoplatelets incorporating iodide and/or bromide halide anions, methylammonium or formamidinium organic cations, and variable organic surface ligands are demonstrated. Procedures for controlling the absorption and emission energy and the thickness purity of the colloidal dispersion are discussed.

<table>
	<tbody>
		<tr>
			<td>Equipment</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>365nm fiber-coupled LED</td>
			<td>Thorlabs</td>
			<td>M365FP1</td>
			<td>Excitation source (Photoluminescence)</td>
		</tr>
		<tr>
			<td>Avantes fiber-optic spectrometer</td>
			<td>Avantes</td>
			<td>AvaSpec-2048XL</td>
			<td>Photoluminescence detector (Photoluminescence spectra)</td>
		</tr>
		<tr>
			<td>Cary 5000</td>
			<td>Agilent Technologies</td>
			<td></td>
			<td>UV-Vis spectrophotometer (Absorption spectra)</td>
		</tr>
		<tr>
			<td>FEI Tecnai G2 Spirit Twin TEM</td>
			<td>FEI Company</td>
			<td></td>
			<td>Transmission electron microscopy (TEM) operating at 120kV</td>
		</tr>
		<tr>
			<td>PANalytical X&#39;Pert Pro MPD</td>
			<td>Malvern Panalytical</td>
			<td></td>
			<td>X-ray diffraction (XRD) operating at 45 kV and 40 mA with a copper radiation source.</td>
		</tr>
		<tr>
			<td>Materials</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>n-butylammonium bromide (BABr)</td>
			<td>GreatCell Solar</td>
			<td>MS305000-50G</td>
			<td></td>
		</tr>
		<tr>
			<td>n-butylammonium chloride (BACl)</td>
			<td>Fisher Scientific</td>
			<td>B071025G</td>
			<td>butylamine hydrochloride</td>
		</tr>
		<tr>
			<td>n-butylammonium iodide (BAI)</td>
			<td>Sigma-Aldrich</td>
			<td>805874-25G</td>
			<td></td>
		</tr>
		<tr>
			<td>N,N-dimethylforamide (DMF)</td>
			<td>Sigma-Aldrich</td>
			<td>227056-1L</td>
			<td>Anhydrous, 99.8%</td>
		</tr>
		<tr>
			<td>n-dodecylammonium bromide (DDABr)</td>
			<td>GreatCell Solar</td>
			<td>MS300880-05</td>
			<td></td>
		</tr>
		<tr>
			<td>formamidinium bromide (FABr)</td>
			<td>GreatCell Solar</td>
			<td>MS350000-100G</td>
			<td></td>
		</tr>
		<tr>
			<td>formamidinium iodide (FAI)</td>
			<td>GreatCell Solar</td>
			<td>MS150000-100G</td>
			<td></td>
		</tr>
		<tr>
			<td>n-hexylammonium bromide (HABr)</td>
			<td>GreatCell Solar</td>
			<td>MS300860-05</td>
			<td></td>
		</tr>
		<tr>
			<td>lead bromide (PbBr2)</td>
			<td>Sigma-Aldrich</td>
			<td>398853-5G</td>
			<td>.99.999%</td>
		</tr>
		<tr>
			<td>lead chloride (PbCl2)</td>
			<td>Sigma-Aldrich</td>
			<td>268-690-5G</td>
			<td>98%</td>
		</tr>
		<tr>
			<td>lead iodide (PbI2) solution</td>
			<td>Sigma-Aldrich</td>
			<td>795550-10ML</td>
			<td>0.55M in DMF</td>
		</tr>
		<tr>
			<td>methylammonium bromide (MABr)</td>
			<td>GreatCell Solar</td>
			<td>MS301000-100G</td>
			<td></td>
		</tr>
		<tr>
			<td>methylammonium iodide (MAI)</td>
			<td>GreatCell Solar</td>
			<td>MS101000-100G</td>
			<td></td>
		</tr>
		<tr>
			<td>n-octylammonium bromide (OABr)</td>
			<td>GreatCell Solar</td>
			<td>MS305500-50G</td>
			<td></td>
		</tr>
		<tr>
			<td>n-octylammonium chloride (OACl)</td>
			<td>Fisher Scientific</td>
			<td>O04841G</td>
			<td>octylamine hydrochloride</td>
		</tr>
		<tr>
			<td>n-octylammonium iodide (OAI)</td>
			<td>GreatCell Solar</td>
			<td>MS105500-50G</td>
			<td></td>
		</tr>
		<tr>
			<td>iso-pentylammonium bromide (i-PABr)</td>
			<td>GreatCell Solar</td>
			<td>MS300710-05</td>
			<td></td>
		</tr>
		<tr>
			<td>toluene</td>
			<td>Sigma-Aldrich</td>
			<td>244511-1L</td>
			<td>Anhydrous, 99.8%</td>
		</tr>
	</tbody>
</table>

facile synthesis of colloidal lead halide perovskite nanoplatelets via ligand-assisted reprecipitation

In this work, we demonstrate a facile method for colloidal lead halide perovskite nanoplatelet synthesis (Chemical formula: L2[ABX3]n-1BX4, L: butylammonium and octylammonium, A: methylammonium or formamidinium, B: lead, X: bromide and iodide, n: number of [BX6]4- octahedral layers in the direction of nanoplatelet thickness) via ligand-assisted reprecipitation. Individual perovskite precursor solutions are prepared by dissolving each nanoplatelet constituent salt in N,N-dimethylformamide (DMF), which is a polar organic solvent, and then mixing in specific ratios for targeted nanoplatelet thickness and composition. Once the mixed precursor solution is dropped into nonpolar toluene, the abrupt change in the solubility induces the instantaneous crystallization of nanoplatelets with surface-bound alkylammonium halide ligands providing colloidal stability. Photoluminescence and absorption spectra reveal emissive and strongly quantum-confined features. X-ray diffraction and transmission electron microscopy confirm the two-dimensional structure of the nanoplatelets. Furthermore, we demonstrate that the band gap of perovskite nanoplatelets can be continuously tuned in the visible range by varying the stoichiometry of the halide ion(s). Lastly, we demonstrate the flexibility of the ligand-assisted reprecipitation method by introducing multiple species as surface-capping ligands. This methodology represents a simple procedure for preparing dispersions of emissive 2D colloidal semiconductors.

Schematic illustration of perovskite nanoplatelets and synthesis procedure gives an overview of the material and synthetic details (Figure 1). Pictures of colloidal perovskite nanoplatelet solutions under ambient light and UV (Figure 2), combined with photoluminescence and absorption spectra (Figure 3) further confirm the emissive and absorptive nature of nanoplatelets. TEM images (Figure 4) and XRD pat...

Watch this Scientific Journal Video about Facile Synthesis of Colloidal Lead Halide Perovskite Nanoplatelets via Ligand-Assisted Reprecipitation at JoVE.com

Facile Synthesis of Colloidal Lead Halide Perovskite Nanoplatelets via Ligand-Assisted Reprecipitation

This work demonstrates facile room-temperature synthesis of colloidal quantum-confined lead halide perovskite nanoplatelets by ligand-assisted reprecipitation method. Synthesized nanoplatelets show spectrally narrow optical features and continuous spectral tunability throughout the visible range by varying the composition and thicknesses.

In this work, we demonstrate a facile method for colloidal lead halide perovskite nanoplatelet synthesis (Chemical formula: L2[ABX3]n-1BX4, L: ...

This protocol demonstrates the room temperature synthesis of colloidal perovskite nanoplatelets for future optoelectronic applications. The main advantage of this approach is the compositional flexibility it provides. By making straightforward changes to the precursor mixtures, different perovskite nanoplatelets can be easily obtained.Lead halide perovskites are uniquely suited to the ligand-assisted reprecipitation method. Unlike traditional semiconductors, the bonds within the perovskite crystal lattice can be easily broken and reformed at room temperature. To synthesize and equals to methylammonium lead bromide nanoplatelets, mix individual one milliliter volumes of the indicated 0.2 molar precursor solutions according to the table.To synthesize and equals to methylammonium lead iodide nanoplatelets, mix individual one milliliter volumes of the indicated 0.2 molar precursor solutions according to the table. To synthesize nanoplatelets with mixed halide compositions, combine bromide only and iodide only perovskite nanoplatelet precursor solutions of the same thickness at the desired volumetric ratio for the target composition. For perovskite nanoplatelet synthesis, inject 10 microliters of each mixed precursor solution into individual 10 milliliter aliquots of toluene under vigorous stirring.Leave the solutions under stirring for 10 minutes until no further color changes are observed to ensure a complete crystallization of each of the perovskite nanoplatelets. For general purification of the perovskite nanoplatelets, centrifuge the solutions at 2, 050 times g for 10 minutes and discard the supernatants. Then, re-disburse the nanoplatelets in an appropriate volume of solvent according to the planned downstream analysis with vortexing.Pictures of colloidal perovskite nanoplatelet solutions under ambient and ultraviolet light combined with photoluminescence and absorption spectra further confirm the emissive and absorptive nature of the nanoplatelets. Transmission electron microscopy images and X-ray defraction patterns can be used to estimate the lateral dimensions and stacking spacings of the nanoplatelets, respectively, while also confirming their two-dimensional structures. Absorption spectra of perovskite nanoplatelet solutions with mixed halides demonstrate the tunability of the band gap.Identical photoluminescence spectra from perovskite nanoplatelets with different ligands demonstrate the compositional flexibility of the organic surface capping species. It must be noted that the precise control of the ratios between individual precursors determines the thickness of the resulting nanoplatelets and ensures their thickness homogeneity. Following the synthesis and purification of the nanoplatelets, post-synthesis processes, such as thin film deposition, polymer encapsulation, and optoelectronic device fabrication can be performed depending on the planned usage.One exciting feature of this synthetic method is its suitability for automated and high through-put experimentation, which can be used to quickly generate large data sets to train predictive computer models. Lead halides are believed to be carcinogenic and the inhalation of organic solvents and nanoparticles can be dangerous. Handle all of the chemicals in a well contained environment.

facile-synthesis-colloidal-lead-halide-perovskite-nanoplatelets-via

Research

JoVE Journal

Chemistry

Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of &#946;-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal &#946;-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (&#8804;1.32), predictable copolymer compositions, and high reproducibility of the polymerizations were observed among the products. Fluorescent polymers are obtained by modifying the glycopolymers with carboxyfluorescein succinimidyl ester targeting the primary amine functional groups on AEMA. Lectin-binding specificities of the resulting glycopolymers are verified by testing with corresponding agarose beads coated with specific glycoepitope recognizing lectins. Because of the ease of the synthesis, the tight control of the product compositions and the good reproducibility of the reaction, this protocol can be translated towards preparation of other RAFT-based glycopolymers with specific structures and compositions, as desired.

An efficient, three-step synthesis of RAFT-based fluorescent glycopolymers, consisting of glycomonomer preparation, copolymerization, and post-modification, is demonstrated. This protocol can be used to prepare RAFT-based statistical glycopolymers with desired structures.

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Facile Preparation of 4-Substituted Quinazoline Derivatives

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted 2-aminobenzophenones and thiourea in the presence of dimethyl sulfoxide (DMSO). This is a unique complementary reaction system in which thiourea undergoes thermal decomposition to form carbodiimide and hydrogen sulfide, where the former reacts with 2-aminobenzophenone to form 4-phenylquinazolin-2(1H)-imine intermediate, whilst hydrogen sulfide reacts with DMSO to give methanethiol or other sulfur-containing molecule which then functions as a complementary reducing agent to reduce 4-phenylquinazolin-2(1H)-imine intermediate into 4-phenyl-1,2-dihydroquinazolin-2-amine. Subsequently, the elimination of ammonia from 4-phenyl-1,2-dihydroquinazolin-2-amine affords substituted quinazoline derivative. This reaction usually gives quinazoline derivative as a single product arising from 2-aminobenzophenone as monitored by GC/MS analysis, along with small amount of sulfur-containing molecules such as dimethyl disulfide, dimethyl trisulfide, etc. The reaction usually completes in 4-6 hr at 160 &#186;C in small scale but may last over 24 hr when carried out in large scale. The reaction product can be easily purified by means of washing off DMSO with water followed by column chromatography or thin layer chromatography.

A protocol for facile preparation of 4-substituted quinazoline derivatives from 2-aminobenzophenones, thiourea and dimethyl sulfoxide is presented.

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

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 ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

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 ...

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, ...

Synthesis of Substrate-Bound Au Nanowires Via an Active Surface Growth Mechanism

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a challenge, as it requires asymmetric growth of symmetric crystals. Here, we report a distinctive synthesis of substrate-bound Au nanowires. This template-free synthesis employs thiolated ligands and substrate adsorption to achieve the continuous asymmetric deposition of Au in solution at ambient conditions. The thiolated ligand prevented the Au deposition on the exposed surface of the seeds, so the Au deposition only occurs at the interface between the Au seeds and the substrate. The side of the newly deposited Au nanowires is immediately covered with the thiolated ligand, while the bottom facing the substrate remains ligand-free and active for the next round of Au deposition. We further demonstrate that this Au nanowire growth can be induced on various substrates, and different thiolated ligands can be used to regulate the surface chemistry of the nanowires. The diameter of the nanowires can also be controlled with mixed ligands, in which another &#34;bad&#34; ligand could turn on the lateral growth. With the understanding of the mechanism, Au nanowire-based nanostructures can be designed and synthesized.

We report a solution-based method to synthesize substrate-bound Au nanowires. By tuning the molecular ligands used during the synthesis, the Au nanowires can be grown from various substrates with different surface properties. Au nanowire-based nanostructures can also be synthesized by adjusting the reaction parameters.

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a ...

Facile Protocol for the Synthesis of Self-assembling Polyamine-based Peptide Amphiphiles (PPAs) and Related Biomaterials

Polyamine-based Peptide Amphiphiles (PPAs) are a new class of self-assembling amphiphilic biomaterials-related to the peptide amphiphiles (PAs). Traditional PAs possess charged amino acids as solubilizing groups (lysine, arginine), which are directly connected to a lipid segment or can contain a linker region made of neutral amino acids. Tuning the peptide sequence of PAs can yield diverse morphologies. Similarly, PPAs possess a hydrophobic segment and neutral amino acids, but also contain polyamine molecules as water solubilizing (hydrophilic) groups. As is the case with PAs, PPAs can also self-assemble into diverse morphologies, including small rods, twisted nano-ribbons, and fused nano-sheets, when dissolved in water. However, the presence of both primary and secondary amines on a single polyamine molecule poses a significant challenge when synthesizing PPAs. In this paper, we show a simple protocol, based on literature precedents, to achieve a facile synthesis of PPAs using solid phase peptide synthesis (SPPS). This protocol can be extended to the synthesis of PAs and other similar systems. We also illustrate the steps that are needed for cleavage from the resin, identification, and purification.

Facile Protocol for the Synthesis of Self-assembling Polyamine-based Peptide Amphiphiles PPAs and Related Biomaterials

The synthesis of polyamine-based peptide amphiphiles (PPAs) is a significant challenge due to the presence of multiple amine nitrogens, which requires judicious use of protecting groups to mask these reactive functionalities. In this paper, we describe a facile method for the preparation of these new class of self-assembling molecules.