Molecular Layer Deposition of Functional Thin Films for Advanced Lithographic Patterning

Photoresist materials comprise one of the main challenges faced by lithography to meet the requirements of electronic device size scaling. Here we report for the first time the use of molecular layer deposition (MLD) to produce photoresist materials with controllable placement of functional moieties. Polyurea resists films are deposited by MLD using urea coupling reactions between 1,4-phenylene diisocyanate (PDIC) and ethylenediamine (ED) or 2,2′-(propane-2,2-diylbis(oxy))diethanamine (PDDE) monomers in a layer-by-layer fashion with a linear growth rate, allowing acid-labile groups to be incorporated into the film at well-controlled positions. The films are deposited with stoichiometric compositions and have highly uniform surface morphology as investigated using atomic force microscopy. We show that acid treatment can cleave the backbone of the polyurea film at positions where the acid-labile groups are embedded. We further show that after soaking the polyurea film with photoacid generator (PAG), it acts as a photoresist material and we present several UV patterning demonstrations. This approach presents a new way to make molecularly designed resist films for lithography

Designing an Air-Stable Interphase on Lithium Metal Anode to Improve Cycling Performance

The application of rechargeable lithium metal batteries is challenged by intractable issues of uncontrollable Li dendrite growth that result in poor cycle life and safety risks. In this work, an air-stable interphase is developed to protect the lithium metal anode (LMA) via a facile solution-based approach. The Ag-embedded fluoride-rich interphase not only creates abundant lithiophilic sites for homogenizing Li nucleation and growth but also resists severe air erosion to protect the LMA beneath and enable decent cycling stability. As a result, the Ag–F-rich interphase enables flat Li deposition on LMA, which is clearly observed in the operando Li plating experiments. Paired with a LiFePO4 cathode (11.8 mg cm–2), the Ag–F-rich interphase-modified LMA enables 300 stable cycles at 0.5 C, delivering a capacity retention ratio as high as 91.4%. Even after being exposed to air for 1 h, the modified LMA still runs smoothly for over 120 cycles with ignorable capacity decay, exhibiting great air stability. This work proves the concept of functionalizing the interphase on the LMA to enable good cycling performance even under severe air erosion

Designing an Air-Stable Interphase on Lithium Metal Anode to Improve Cycling Performance

The application of rechargeable lithium metal batteries is challenged by intractable issues of uncontrollable Li dendrite growth that result in poor cycle life and safety risks. In this work, an air-stable interphase is developed to protect the lithium metal anode (LMA) via a facile solution-based approach. The Ag-embedded fluoride-rich interphase not only creates abundant lithiophilic sites for homogenizing Li nucleation and growth but also resists severe air erosion to protect the LMA beneath and enable decent cycling stability. As a result, the Ag–F-rich interphase enables flat Li deposition on LMA, which is clearly observed in the operando Li plating experiments. Paired with a LiFePO4 cathode (11.8 mg cm–2), the Ag–F-rich interphase-modified LMA enables 300 stable cycles at 0.5 C, delivering a capacity retention ratio as high as 91.4%. Even after being exposed to air for 1 h, the modified LMA still runs smoothly for over 120 cycles with ignorable capacity decay, exhibiting great air stability. This work proves the concept of functionalizing the interphase on the LMA to enable good cycling performance even under severe air erosion

Designing an Air-Stable Interphase on Lithium Metal Anode to Improve Cycling Performance

The application of rechargeable lithium metal batteries is challenged by intractable issues of uncontrollable Li dendrite growth that result in poor cycle life and safety risks. In this work, an air-stable interphase is developed to protect the lithium metal anode (LMA) via a facile solution-based approach. The Ag-embedded fluoride-rich interphase not only creates abundant lithiophilic sites for homogenizing Li nucleation and growth but also resists severe air erosion to protect the LMA beneath and enable decent cycling stability. As a result, the Ag–F-rich interphase enables flat Li deposition on LMA, which is clearly observed in the operando Li plating experiments. Paired with a LiFePO4 cathode (11.8 mg cm–2), the Ag–F-rich interphase-modified LMA enables 300 stable cycles at 0.5 C, delivering a capacity retention ratio as high as 91.4%. Even after being exposed to air for 1 h, the modified LMA still runs smoothly for over 120 cycles with ignorable capacity decay, exhibiting great air stability. This work proves the concept of functionalizing the interphase on the LMA to enable good cycling performance even under severe air erosion

DataSheet_1_Gene expression variations and allele-specific expression of two rice and their hybrid in caryopses at single-nucleus resolution.docx

Seeds are an indispensable part of the flowering plant life cycle and a critical determinant of agricultural production. Distinct differences in the anatomy and morphology of seeds separate monocots and dicots. Although some progress has been made with respect to understanding seed development in Arabidopsis, the transcriptomic features of monocotyledon seeds at the cellular level are much less understood. Since most important cereal crops, such as rice, maize, and wheat, are monocots, it is essential to study transcriptional differentiation and heterogeneity during seed development at a finer scale. Here, we present single-nucleus RNA sequencing (snRNA-seq) results of over three thousand nuclei from caryopses of the rice cultivars Nipponbare and 9311 and their intersubspecies F1 hybrid. A transcriptomics atlas that covers most of the cell types present during the early developmental stage of rice caryopses was successfully constructed. Additionally, novel specific marker genes were identified for each nuclear cluster in the rice caryopsis. Moreover, with a focus on rice endosperm, the differentiation trajectory of endosperm subclusters was reconstructed to reveal the developmental process. Allele-specific expression (ASE) profiling in endosperm revealed 345 genes with ASE (ASEGs). Further pairwise comparisons of the differentially expressed genes (DEGs) in each endosperm cluster among the three rice samples demonstrated transcriptional divergence. Our research reveals differentiation in rice caryopsis from the single-nucleus perspective and provides valuable resources to facilitate clarification of the molecular mechanism underlying caryopsis development in rice and other monocots.</p

DataSheet_2_Gene expression variations and allele-specific expression of two rice and their hybrid in caryopses at single-nucleus resolution.xlsx

Seeds are an indispensable part of the flowering plant life cycle and a critical determinant of agricultural production. Distinct differences in the anatomy and morphology of seeds separate monocots and dicots. Although some progress has been made with respect to understanding seed development in Arabidopsis, the transcriptomic features of monocotyledon seeds at the cellular level are much less understood. Since most important cereal crops, such as rice, maize, and wheat, are monocots, it is essential to study transcriptional differentiation and heterogeneity during seed development at a finer scale. Here, we present single-nucleus RNA sequencing (snRNA-seq) results of over three thousand nuclei from caryopses of the rice cultivars Nipponbare and 9311 and their intersubspecies F1 hybrid. A transcriptomics atlas that covers most of the cell types present during the early developmental stage of rice caryopses was successfully constructed. Additionally, novel specific marker genes were identified for each nuclear cluster in the rice caryopsis. Moreover, with a focus on rice endosperm, the differentiation trajectory of endosperm subclusters was reconstructed to reveal the developmental process. Allele-specific expression (ASE) profiling in endosperm revealed 345 genes with ASE (ASEGs). Further pairwise comparisons of the differentially expressed genes (DEGs) in each endosperm cluster among the three rice samples demonstrated transcriptional divergence. Our research reveals differentiation in rice caryopsis from the single-nucleus perspective and provides valuable resources to facilitate clarification of the molecular mechanism underlying caryopsis development in rice and other monocots.</p

Area Selective Molecular Layer Deposition of Polyurea Films

Patterned organic thin films with submicrometer features are of great importance in applications such as nanoelectronics and optoelectronics. We present here a new approach for creating patterned organic films using area selective molecular layer deposition (MLD). MLD is a technique that allows for conformal deposition of nanoscale organic thin films with exceptional control over vertical thickness and composition. By expanding the technique to allow for area selective MLD, lateral patterning of the film can be achieved. In this work, polyurea thin films were deposited by alternating pulses of 1,4-phenylenediisocyanate (PDIC) and ethylenediamine (ED) in a layer-by-layer fashion with a linear growth rate of 5.3 Å/cycle. Studies were carried out to determine whether self-assembled monolayer (SAM) formed from octadecyltrichlorosilane (ODTS) could block MLD on silicon substrates. Results show that the MLD process is impeded by the SAM. To test lateral patterning in MLD, SAMs were patterned onto silicon substrates using two different approaches. In one approach, SiO₂-coated Si(100) substrates were patterned with an ODTS SAM by soft lithography in a well-controlled environment. In the second approach, patterned ODTS SAM was formed on H–Si/SiO₂ patterned wafers by employing the chemically selective adsorption of ODTS on SiO₂ over H–Si. Auger electron spectroscopy results revealed that the polyurea film is deposited predominantly on the ODTS-free regions of both patterned substrates, indicating sufficient blocking of MLD by the ODTS SAM layer to replicate the pattern. The method we describe here offers a novel approach for fabricating high quality, three-dimensional organic structures

As Fig 13, but now for a system with halved lattice spacing.

<p>As <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0147206#pone.0147206.g013" target="_blank">Fig 13</a>, but now for a system with halved lattice spacing.</p

Results of an LBM calculation for a lid-driven cavity, with the geometry (a), streamlines (b), and normalized velocity components <i>u</i>/<i>u</i>₀ (c) and <i>v</i>/<i>u</i>₀ (d).

<p>Results of an LBM calculation for a lid-driven cavity, with the geometry (a), streamlines (b), and normalized velocity components <i>u</i>/<i>u</i>₀ (c) and <i>v</i>/<i>u</i>₀ (d).</p

Cross-Linked Ultrathin Polyurea Films via Molecular Layer Deposition

Ultrathin cross-linked polymer thin films are highly desirable materials because of their important roles in many applications. However, they are difficult and challenging to fabricate. Here we report a one-step process for depositing cross-linked polyurea thin films using a vapor-phase molecular layer deposition (MLD) technique. 1,4-Diisocyanatobutane and a series of different multiamines, including diethylenetriamine, triethylenetetramine, and tris­(2-aminoethyl)­amine, were used to grow polyurea MLD films via urea-coupling reactions. The deposited cross-linked polyurea films exhibit characteristic MLD film growth behaviors, such as constant growth rates, infrared absorption by expected urea modes, and stoichiometric chemical compositions. More importantly, the cross-linking is shown to be capable of improving the film properties. Based on cross-linking, the thin film density can be increased by approximately 50%. In addition, the film decomposition temperature is increased by about 30 °C, suggesting an enhanced thermal stability of the cross-linked ultrathin polyurea films