MRSEC Research Data
Persistent link for this collectionhttps://hdl.handle.net/11299/214081
Search within MRSEC Research Data
Browse
Recent Submissions
Item Supporting Data for Circular Dichroism of Distorted Double Gyroid Thin Film Metamaterials(2024-11-04) McGuinness, Emily; Magruder, Benjamin; Dorfman, Kevin; Ellison, Chris; Ferry, Vivian; veferry@umn.edu; Ferry, Vivian; Department of Chemical Engineering and Materials Science, University of MinnesotaStrong circular dichroism (CD) has been reported in triply periodic, co-continuous gyroid thin films for certain orientations and surface terminations. However, processing of gyroid thin films introduces distortions experimentally, creating a mismatch between the structures created practically and those explored computationally. This work explores the impact of compression normal to the substrate (z-compression) with conserved volume in (110)-oriented plasmonic silver double gyroid thin films on CD using finite-difference time-domain (FDTD) simulations. As compression reaches fifteen percent and above, new features emerge including termination-dependent opposite-handed CD responses and, at larger compressions, shorter wavelength responses that span many surface terminations. The longest wavelength responses of the system red-shift with increasing compression. The top surface structure contributes strongly to the emerging opposite-handed features and red-shifting of wavelengths. However, the less surface termination dependent features arise from a mixture of contributions from the top surface and interior of the films. Interplay of these leads to CD-switching phenomena as a function of compression for certain terminations and wavelengths. When alternative methods are utilized to compress the system, such as compression with a Poisson’s ratio of 0.33 (comparable to polystyrene) or the generation of compressed equilibrium structures with non-affine strut changes via self-consistent field theory, similar optical responses persist. Overall, this study highlights the significant impact experimentally relevant distortions (especially compression and some non-affine structural shifts) can have on the CD response of block copolymer templated plasmonic double gyroid thin films, and provides mechanistic insight into the film interior versus surface contributions to the CD response during compression.Item Data for Combining photocontrolled-cationic and anionic-group transfer polymerizations using a universal mediator: enabling access to two- and three-Mechanism block copolymers(2024-08-15) Hosford, Brandon M; Ramos, William; Lamb, Jessica R; jrlamb@umn.edu; Lamb, Jessica R; Lamb Research GroupAn ongoing challenge in polymer chemistry is accessing diverse block copolymers from multiple polymerization mechanisms and monomer classes. One strategy to accomplish this goal without intermediate compatibilization steps is the use of universal mediators. Thiocarbonyl thio (TCT) functional groups are well-known mediators to combine radical with either cationic or anionic polymerization, but a sequential cationic-anionic universal mediator system has never been reported. Herein, we report a TCT universal mediator that can sequentially perform photocontrolled cationic polymerization and thioacyl anionic group transfer polymerization to access poly(ethyl vinyl ether)-block-poly(thiirane) polymers for the first time. Thermal analyses of these block copolymers provide evidence of microphase separation. The success of this system, along with the established compatibility of radical polymerization, enabled us to further chain extend the cationic-anionic diblock using radical polymerization of N-isopropylacrylamide. The resulting terpolymer represents the first example of a triblock made from three different monomer classes incorporated via three different mechanisms without any end-group modification steps. The development of this simple, sequential synthesis using a universal mediator approach opens up new possibilities by providing facile access to diverse block copolymers of vinyl ethers, thiiranes, and acrylamides.Item Data for Equilibrium Phase Behavior of Gyroid-Forming Diblock Polymer Thin Films(2024-08-08) Magruder, Benjamin; Ellison, Christopher; Dorfman, Kevin; dorfman@umn.edu; Dorfman, Kevin; Dorfman Research GroupThe dataset contains the results of thin-film self-consistent field theory calculations for the double-gyroid phase and other related phases in AB diblock polymers. All results used to construct the figures in the referenced manuscript are included in this dataset, along with many of the scripts used to perform the analysis in the manuscript. To reduce the size of the dataset, we opted to include only the first and last field file in each parameter sweep, though we kept the corresponding summary file at every state point in every sweep, and included all necessary input files to regenerate the data if desired. The PSCF software package (C++ version) was used to generate this dataset (https://github.com/dmorse/pscfpp).Item Data for Wavelength Dependence of Plasmon-Induced Vibrational Energy Transfer in Fluorophore–Plasmonic Systems(2024-08-01) Christenson, Gerrit N; Yu, Ziwei; Frontiera, Renee R; rrf@umn.edu; Frontiera, Renee R; Materials Research Science & Engineering CenterUnderstanding, predicting, and controlling plasmon–molecule energy transfer are important for improvements to plasmonic photocatalysis and photothermal therapies. Here, we use continuous wave surface-enhanced anti-Stokes and Stokes Raman spectroscopy to quantify the vibrational kinetic energy, equivalent to a molecular temperature under a Boltzmann approximation, of Raman-active vibrational modes of molecules at plasmonic interfaces. In previous work from our group, we observed an anomalous steady-state reduction in vibrational kinetic energies in benzenethiols absorbed onto the surface of gold nanoparticles. To further explore this effect, here, we quantify the wavelength dependence of vibrational energy in plasmon–fluorophore systems, where molecules can undergo electronic transitions with resonant excitation. We used three excitation wavelengths and three molecules with varying electronic resonance energies. We observe wavelength-dependent vibrational energy distributions, which we attribute to competing effects of on-resonance heating and off-resonance decrease in the population ratio. This work thus quantifies the resonance wavelength dependence of vibrational energy in plasmon molecular systems and helps to suggest future applications of tailored systems with controllable energy transfer pathways.Item Data for Chain and Structural Dynamics in Melts of Sphere-Forming Diblock Copolymers(2024-07-22) Chawla, Anshul; Bates, Frank S; Dorfman, Kevin D; Morse, David C; dorfman@umn.edu; Dorfman, Kevin D; Dorfman Research GroupProcessed simulation data appearing in the related manuscriptItem Supporting Data for Self-Assembly of Unusually Stable Thermotropic Network Phases by Cellobiose-Based Guerbet Glycolipids(2024-04-08) Das, Soumi; Zheng, Caini; Calabrese, Michelle A; Reineke, Theresa M; Siepmann, Ilja J; Mahanthappa, Mahesh K; Lodge, Timothy P; treineke@umn.edu; Reineke, Theresa M; University of MinnesotaThese files contain data along with associated output from instrumentation supporting all results reported in the referenced paper. Bicontinuous thermotropic liquid crystal (LC) materials, such as double gyroid (DG) phases, are highly promising for various applications due to their intricate 3D network structures. However, the lack of robust molecular design rules for shape-filling amphiphiles hinders their utility. To address this, we synthesized cellobiose-based glycolipids with Guerbet-type branched alkyl tails and examined their thermotropic LC self-assembly. Through techniques including differential scanning calorimetry (DSC), polarized optical microscopy (POM), and small-angle X-ray scattering (SAXS), we found that Guerbet cellobiosides have a strong propensity to form DG morphology across broad thermotropic phase ranges. The stability of these assemblies depends on the alkyl tail structure and anomeric configuration of the glycolipid in a previously unrecognized manner. Molecular simulations provide further insights, revealing molecular motifs crucial for network phase self-assembly, paving the way for future designs and applications of network LC materials.Item Supporting data for Crosslinked polyolefins through tandem ROMP/hydrogenation(2024-03-14) Hillmyer, Marc A; Sample, Caitlin S; Hoehn, Brenden D; hillmyer@umn.edu; Hillmyer, Marc A; Hillmyer Research GroupThese files contain primary data along with associated output from instrumentation supporting all results reported in Sample et al. "Crosslinked Polyolefins Through Tandem ROMP/Hydrogenation". Crosslinked polyolefins have important advantages over their thermoplastic analogues, particularly improved impact strength and abrasion resistance, as well as increased chemical and thermal stability; however, most strategies for their production involve post-polymerization crosslinking of polyolefin chains. Here, a tandem ring-opening metathesis polymerization (ROMP)/hydrogenation approach is presented. Cyclooctene (COE)-co-dicyclopentadiene (DCPD) networks are first synthesized using ROMP, after which the dispersed Ru metathesis catalyst is activated for hydrogenation through addition of hydrogen gas. The reaction temperature for hydrogenation must be sufficiently high to allow mobility within the system, as dictated by thermal transitions (i.e., glass and melting transitions) of the polymeric matrix. COE-rich materials exhibit branched-polyethylene-like crystallinity (25% crystallinity) and melting points (Tm = 107 °C), as well as excellent ductility (>750 % extension), while majority DCPD materials are glassy (Tg = 84 °C) and much stiffer (E = 710 MPa); all materials exhibit high tensile toughness. Importantly, hydrogenation of olefins in these crosslinked materials leads to notable improvements in oxidative stability, as saturated networks do not experience the same substantial degradation of mechanical performance as their unsaturated counterparts upon prolonged exposure to air at high temperature.Item Data for Boundary Frustration in Double-Gyroid Thin Films(2024-02-29) Magruder, Benjamin R; Morse, David C; Ellison, Christopher J; Dorfman, Kevin D; dorfman@umn.edu; Dorfman, Kevin D; Dorfman Group, UMN CEMSWe have used self-consistent field theory to predict the morphology and preferred orientation of the double-gyroid phase in thin films of AB diblock polymers. A manuscript has been submitted containing this data, and is expected to appear shortly. The data were generated using the C++ version of the open-source software PSCF (https://pscf.cems.umn.edu/). All input and output files from PSCF used to generate the data in the paper are included in this dataset, as well as the code used to process the data and generate the figures.Item Data for Magnetization dynamics in synthetic antiferromagnets with perpendicular magnetic anisotropy(2023-11-09) Huang, Dingbin; Zhang, Delin; Kim, Yun; Wang, Jian-Ping; Wang, Xiaojia; wang4940@umn.edu; Wang, Xiaojia; Materials Research Science & Engineering CenterThis repository contains data along with associated output from instrumentation supporting all results reported in Huang, D.; Zhang, D.; Kim, Y; Wang, J.P.; and Wang X. Magnetization dynamics in synthetic antiferromagnets with perpendicular magnetic anisotropy. Phys. Rev. B., 2023, 107, 214438. The magnetization dynamics of the perpendicular synthetic antiferromagnets (p-SAFs) sample is detected by time-resolved magneto-optical Kerr effect (TR-MOKE), which is ultrafast-laser-based metrology utilizing a pump-probe configuration. In TR-MOKE, pump laser pulses interact with the sample, initiating magnetization dynamics in magnetic layers via inducing ultrafast thermal demagnetization. The laser-induced heating brings a rapid decrease to the magnetic anisotropy fields and interlayer exchange coupling (IEC), which changes equilibrium direction of magnetization in each layer and initiates the precession. The magnetization dynamics due to pump excitation is detected by a probe beam through MOKE. In our setup, the incident probe beam is normal to the sample surface (polar MOKE); therefore, the Kerr rotation angle (θ_K) of the reflected probe beam is proportional to the z component of the magnetization.Item Data for Crystal-Chemical Origins of the Ultrahigh Conductivity of Metallic Delafossites(2023-11-09) Zhang, Yi; Tutt, Fred; Evans, Guy N; Sharma, Prachi; Haugstad, Greg; Kaiser, Ben; Ramberger, Justin; Bayliff, Samuel; Tao, Yu; Manno, Mike; Garcia-Barriocanal, Javier; Chaturvedi, Vipul; Fernandes, Rafael M; Birol, Turan; Seyfried Jr, William E; Leighton, Chris; leighton@umn.edu; Leighton, Chris; Leighton Electronic and Magnetic Materials LabDespite their highly anisotropic complex-oxidic nature, certain delafossite compounds (e.g., PdCoO2, PtCoO2) are the most conductive oxides known, for reasons that remain poorly understood. Their room-temperature conductivity can exceed that of Au, while their low-temperature electronic mean-free-paths reach an astonishing 20 um. It is widely accepted that these materials must be ultrapure to achieve this, although the methods for their growth (which produce only small crystals) are not typically capable of such. Here, we first report a new approach to PdCoO2 crystal growth, using chemical vapor transport methods to achieve order-of-magnitude gains in size, the highest structural qualities yet reported, and record residual resistivity ratios (>440). Nevertheless, the first detailed mass spectrometry measurements on these materials reveal that they are not ultrapure, typically harboring 100s-of-parts-per-million impurity levels. Through quantitative crystal-chemical analyses, we resolve this apparent dichotomy, showing that the vast majority of impurities are forced to reside in the Co-O octahedral layers, leaving the conductive Pd sheets highly pure (~1 ppm impurity concentrations). These purities are shown to be in quantitative agreement with measured residual resistivities. We thus conclude that a previously unconsidered “sublattice purification” mechanism is essential to the ultrahigh low-temperature conductivity and mean-free-path of metallic delafossites. This dataset contains all digital data in the published paper of the same name.Item Supporting data for Temperature-dependent thermal conductivity of MBE-grown epitaxial SrSnO₃ films(2023-11-06) Zhang, Chi; Liu, Fengdeng; Guo, Silu; Zhang, Yingying; Xu, Xiaotian; Mkhoyan, Andre; Jalan, Bharat; Wang, Xiaojia; wang4940@umn.edu; Wang, Xiaojia; Materials Research Science & Engineering CenterThis work studies the temperature-dependent thermal properties of a single crystalline SSO thin film prepared with hybrid molecular beam epitaxy. By combining time-domain thermoreflectance and Debye–Callaway modeling, physical insight into thermal transport mechanisms is provided. At room temperature, the 350-nm SSO film has a thermal conductivity of 4.4 W m¯¹ K¯¹ , ∼60% lower than those of other perovskite oxides (SrTiO₃, BaSnO₃) with the same ABO₃ structural formula. This difference is attributed to the low zone-boundary frequency of SSO, resulting from its distorted orthorhombic structure with tilted octahedra. At high temperatures, the thermal conductivity of SSO decreases with temperature following a ∼T ¯⁰∙⁵⁴ dependence, weaker than the typical T¯¹ trend dominated by the Umklapp scattering. Corresponding author for STEM data is K. Andre Mkhoyan. Corresponding author for film growth and XRD data is Bharat Jalan. Corresponding author for TDTR data is Xiaojia Wang.Item Data for Gaming self-consistent field theory: Generative block polymer phase discovery(2023-10-18) Chen, Pengyu; Dorfman, Kevin D; dorfman@umn.edu; Dorfman, Kevin D; Dorfman Research Group - University of Minnesota Department of Chemical Engineering and Materials ScienceThis dataset contains the input and output files for self-consistent field theory (SCFT) simulations and the training of generative adversarial networks (GANs) in the associated paper.Item Data for Single Gyroid in H-shaped Block Copolymers(2023-10-05) Park, Sojung; Bates, Frank S; Dorfman, Kevin D; dorfman@umn.edu; Dorfman, Kevin D; Dorfman Research Group - University of Minnesota Department of Chemical Engineering and Materials ScienceThis data set contains the input and output files from the PSCF C++ program used for the self-consistent field theory (SCFT) simulation in "Single Gyroid in H-shaped Block Copolymers." Self-consistent field theory was used to investigate the equilibrium phase behavior of H-shaped block copolymers. With this dataset, users should be able to regenerate all the calculations that appeared in the paper, using the open-source C++ SCFT program available on GitHub (https://github.com/dmorse/pscfpp).Item Data for Surface Relief Terraces in Double Gyroid-Forming Polystyrene-block-Polylactide Thin Films(2023-09-28) Yang, Szu-Ming; Oh, Jinwoo; Magruder, Benjamin R; Kim, HeeJoong; Dorfman, Kevin D; Mahanthappa, Mahesh K; Ellison, Christopher J; cellison@umn.edu; Ellison, Christopher J; University of Minnesota Department of Chemical Engineering and Materials ScienceThis study describes the thin film self-assembly behavior of a polystyrene-block-polylactide (SL-G) diblock copolymer, which undergoes melt self-assembly in bulk into a double gyroid (DG) network phase with a cubic unit cell parameter a = 52.7 nm. Scanning electron microscopy (SEM) and grazing-incidence small-angle X-ray scattering (GISAXS) reveal that thermally annealing 140–198 nm thick copolymer films on SiO2 substrates below the morphological order-to-disorder transition temperature yields polydomain DG structures, in which the (422) planes are oriented parallel to the surface. Bright-field optical microscopy (OM) and atomic force microscopy (AFM) analyses further reveal the film thickness-dependent formation of topographical terraces, including islands, holes, and bicontinuous features. The occurrence of these features sensitively depends on the incommensurability of the as-prepared film thickness and the (211)-interplanar spacing (d211) of the DG unit cell. While the steps heights between adjacent terraces exhibiting characteristic “double wave” patterns of the DG (422) planes coincide with d211, previously unreported transition zones between adjacent terraces are observed wherein “boomerang” and “droplet” patterns are observed. These intermediate patterns follow the expected sequence of adjacent termination planes of the bulk DG unit cell along the [211] direction, as confirmed by comparisons with self-consistent mean-field theory calculations.Item Supporting data for Mending Cracks Atom-by-atom in Rutile TiO2 with Electron Beam Radiolysis(2023-08-28) Guo, Silu; Yun, Hwanhui; Nair, Sreejith; Jalan, Bharat; Mkhoyan, K. Andre; mkhoyan@umn.edu; Mkhoyan, K. Andre; Materials Research Science & Engineering CenterExperimental data for a manuscript "Mending Cracks Atom-by-atom in Rutile TiO2 with Electron Beam Radiolysis". Essential data includes scanning transmission electron microscopy (STEM) raw images and electron energy-loss spectroscopy (EELS) spectrum data. Important atomic line scans data and radiolysis cross section data file are included to support our “two-step rolling” model of mobile octahedral building blocks enabling radiolysis-driven atomic migration.Item Data for Threading-the-Needle: Compatibilization of HDPE/iPP blends with butadiene-derived polyolefin block copolymers(2023-07-31) Shen, Liyang; Diaz Gorbea, Gabriela; Danielson, Evan; Cui, Shuquan; Ellison, Christopher J; Bates, Frank S; bates001@umn.edu; Bates, Frank S; University of Minnesota Department Chemical Engineering and Material ScienceManagement of the plastic industry is a momentous challenge, one that pits enormous societal benefits against an accumulating reservoir of nearly indestructible waste. A promising strategy for recycling polyethylene (PE) and isotactic polypropylene (iPP), constituting roughly half the plastic produced annually worldwide, is melt blending for reformulation into useful products. Unfortunately, such blends are generally brittle and useless due to phase separation and mechanically weak domain interfaces. Recent studies have shown that addition of small amounts of semicrystalline PE-iPP block copolymers (ca. 1 wt%) to mixtures of these polyolefns results in ductility comparable to the pure materials. However, current methods for producing such additives rely on expensive reagents, prohibitively impacting the cost of recycling these inexpensive commodity plastics. Here, we describe an alternative strategy that exploits anionic polymerization of butadiene into block copolymers, with subsequent catalytic hydrogenation, yielding E and X blocks that are individually melt miscible with PE and iPP, where E and X are poly(ethylene-ran-ethylethylene) random copolymers with 6% and 90% ethylethylene repeat units, respectively. Cooling melt blended mixtures of PE and iPP containing 1 wt% of the triblock copolymer EXE of appropriate molecular weight, results in mechanical properties competitive with the component plastics. Blend toughness is obtained through interfacial topological entanglements of the amorphous X polymer and semicrystalline iPP, along with anchoring of the E blocks through cocrystallization with the PE homopolymer. Significantly, EXE can be inexpensively produced using currently practiced industrial scale polymerization methods, offering a practical approach to recycling the world’s top two plastics.Item Supporting data for Core−Shell Gyroid in ABC Bottlebrush Block Terpolymers(2023-05-25) Cui, Shuquan; Zhang, Bo; Shen, Liyang; Bates, Frank S; Lodge, Timothy P; lodge@umn.edu; Lodge, Timothy P; University of Minnesota Department of ChemistryThese files contain primary data supporting all results reported in Cui et al. "Core−shell gyroid in ABC bottlebrush block terpolymers." A series of bottlebrush block polymers containing 24 PEP-PS diblock copolymers and 109 PEP-PS-PEO triblock terpolymers were synthesized by ring-opening metathesis polymerization (ROMP) of norbornene-functionalized poly(ethylene-alt-propylene) (PEP), poly(styrene) (PS), and poly(ethylene oxide) (PEO) macromonomers. The molecular weights of the three macromonomers were around 1 kg/mol. The relatively modest total backbone degrees of polymerization ranged from ca. 20 to 40. Morphologies of these bottlebrush block polymers were characterized by small-angle X-ray scattering (SAXS). The PEP-PS diblocks exhibited only cylindrical (HEX) and lamellar (LAM) morphologies; the desired network phases did not appear in these materials, consistent with previous experimental studies. However, adding variable-length bottlebrush PEO blocks to diblocks containing 30% to 50% PS led to a substantial core-shell double gyroid (GYR) phase window in the ternary phase portrait. Encouragingly, the GYR unit cell dimensions increased almost linearly with the backbone degree of polymerization, portending the ability to access larger network dimensions than previously obtained with linear block polymers. This finding demonstrates a periodic network phase in bottlebrush block polymers for the first time and highlights extraordinary opportunities associated with applying facile ROMP chemistry to multiblock bottlebrush polymers.Item Supporting data for Wide-range continuous tuning of the thermal conductivity of La0.5Sr0.5CoO3−δ films via room-temperature ion-gel gating(2023-04-19) Zhang, Yingying; Postiglione, William M; Xie, Rui; Zhang, Chi; Zhou, Hao; Chaturvedi, Vipul; Heltemes, Kei; Zhou, Hua; Feng, Tianli; Leighton, Chris; Wang, Xiaojia; wang4940@umn.edu; Wang, Xiaojia; Materials Research Science & Engineering CenterThese files contain data along with associated output from instrumentation supporting all results reported in Wide-range continuous tuning of the thermal conductivity of La0.5Sr0.5CoO3-delta films via room-temperature ion-gel gating. Solid-state control of the thermal conductivity of materials is of exceptional interest for novel devices such as thermal diodes and switches. Here, we demonstrate the ability to continuously tune the thermal conductivity of nanoscale films of La0.5Sr0.5CoO3-delta (LSCO) by a factor of over 5, via a room-temperature electrolyte-gate-induced non-volatile topotactic phase transformation from perovskite (with ≈ 0.1) to an oxygen-vacancy-ordered brownmillerite phase (with = 0.5), accompanied by a metal-insulator transition. Combining time-domain thermoreflectance and electronic transport measurements, model analyses based on molecular dynamics and Boltzmann transport, and structural characterization by X-ray diffraction, we uncover and deconvolve the effects of these transitions on heat carriers, including electrons and lattice vibrations. The wide-range continuous tunability of LSCO thermal conductivity enabled by low-voltage (below 4 V) room-temperature electrolyte gating opens the door to non-volatile dynamic control of thermal transport in perovskite-based functional materials, for thermal regulation and management in device applications. Authors to whom correspondence should be addressed are Chris Leighton (leighton@umn.edu) and Xiaojia Wang (wang4940@umn.edu).Item Structural and chemical characterization data for Ir and Ru metal/metal-oxide thin films showing strain dependence of metal oxidation(2023-04-05) Nair, Sreejith T; Yang, Zhifei; Lee, Dooyong; Guo, Silu; Sadowski, Jerzy T; Johnson, Spencer; Saboor, Abdul; Li, Yan; Zhou, Hua; Comes, Ryan B; Jin, Wencan; Mkhoyan, Andre K; Janotti, Anderson; Jalan, Bharat; nair0074@umn.edu; Nair, Sreejith T; University of Minnesota Jalan MBE LabIn this work, the authors uncover a previously unexplored effect of substrate imposed epitaxial strain on the formation energy of a crystalline epitaxial metal oxide thin film, thereby revealing an additional tuning knob to engineer synthesis of oxide thin films of hard-to-oxidize metals.Item Data for Alternating Gyroid Stabilized by Surfactant-like Triblock Terpolymers in IS/SO/ISO Ternary Blends(2023-03-22) Chen, Pengyu; Bates, Frank S; Dorfman, Kevin D; dorfman@umn.edu; Dorfman, Kevin, D; Dorfman Research Group - University of Minnesota Department of Chemical Engineering and Materials ScienceThis dataset contains the self-consistent field theory (SCFT) simulation results in the associated paper (https://doi.org/10.1021/acs.macromol.2c02485)