Tobin j marks department of chemistry and the materials research center northwestern university
Download
1 / 38

Tobin J. Marks Department of Chemistry and The Materials Research Center Northwestern University - PowerPoint PPT Presentation


  • 239 Views
  • Uploaded on

Tobin J. Marks Department of Chemistry and The Materials Research Center Northwestern University. Charles E. and Emma H. Morrison Professor of Chemistry Professor of Materials Science and Engineering Vladimir N. Ipatieff Professor of Catalyic Chemistry. Biographical sketch.

loader
I am the owner, or an agent authorized to act on behalf of the owner, of the copyrighted work described.
capcha
Download Presentation

PowerPoint Slideshow about 'Tobin J. Marks Department of Chemistry and The Materials Research Center Northwestern University' - haley


An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.


- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -
Presentation Transcript
Tobin j marks department of chemistry and the materials research center northwestern university l.jpg

Tobin J. MarksDepartment of Chemistry and The Materials Research CenterNorthwestern University

Charles E. and Emma H. Morrison Professor of Chemistry

Professor of Materials Science and Engineering

Vladimir N. Ipatieff Professor of Catalyic Chemistry


Biographical sketch l.jpg
Biographical sketch

  • BS, University of Maryland, 1966

  • PhD, Massachusetts Institute of Technology, 1970, under Professor F. A. Cotton.

  • Assistant Professor at Northwestern University, 1970.

  • Numerous awards and honors.

  • Fellow, Royal Society of Chemistry

  • Member, National Academy of Sciences

Published over 800 research articles and holds 80 U.S. patents.


Research activity l.jpg
Research Activity

  • Organometallics

  • Photonics

  • MOCVD

  • Molecular Electronics


Organometallics l.jpg
Organometallics

  • Investigate the Design and Implementation of Organometallic and Main Group Complexes for Catalysis

  • Hydroelementation: Organo-f-element complexes for small-molecule catalysis

  • Olefin polymerization: Nuclearity effects in group 4 and group 13 catalyst/cocatalyst studies


Hydroelementation l.jpg
Hydroelementation

Very desirable yet challenging atom-economical transformation.

Transition Metals:

  • Impressive functional group tolerance

  • High temperatures and catalyst decomposition

    Lanthanide Metals:

  • Efficient at room temperature with long catalyst life

  • Improving (but limited) functional group tolerance.


Lanthanide catalyzed hydroamination l.jpg
Lanthanide Catalyzed Hydroamination

  • Aminoalkene/alkyne hydroamination/ cyclization:

Rate = k[substrate]0[Ln]1

  • Very sensitive to stericdemands around metal center;



Characteristics of hydroamination l.jpg
Characteristics of Hydroamination

Hydroamination carried out on:

1,2-disubstituted internal aminoalkene, aminoallene and aminodiene.

Identical rate law for all substrates.

Rate:La>Sm>Lu (aminoalkenes).

Rate decreasing with increasing Ln3+ radius (aminoalkynes) and maximize at intermediate radius for aminoallenes (Y3+ >Sm3+ >Lu3+ >La3+ ).



Catalyst development chiral catalysts enantioselective hydroamination l.jpg
Catalyst Development:Chiral Catalysts; Enantioselective Hydroamination


Chiral catalyst c 2 symmetric system l.jpg
Chiral Catalyst: C2-symmetric system

Lanthanides having the largest ionic radii exhibit the greatest turnover frequencies as well as enantioselectivities.

Exhibits good rates and enantioselectivities, comparable

to or greater than those achieved with chiral C1-

symmetric organolanthanocene catalysts.



Molecular electronics l.jpg
Molecular Electronics B, H, P)

  • Research involves synthesis and study of thin-film and molecular electronic materials, focusing on the versatile thiophene-based oligomers and polymers as semiconducting and conducting layers.

  • Utilize thin film deposition techniques like spin-coating, sublimation and unique self-assembly.

  • Addressing fundamental questions of electronic structure, optical properties and charge-transport mechanism in these materials through combined synthetic and theoretical research in collaboration with Prof. Ratner.


Molecular electronics14 l.jpg

OLED/PLED B, H, P)

Toward the Ideal Organic Light-Emitting Diode; nanoscale tailoring of the anode/HTL interfaces.

OTFT

Toward N-type semiconductors

Gate dielectrics for low-voltage Organic Field Effect Transistors.

Molecular Electronics


Organic light emitting diode l.jpg
Organic Light Emitting Diode B, H, P)

  • Schematic of a typical OLED heterostructure.

  • (II)Energy level diagram of a typical multilayer OLED. A and B indicate the cathode-ETL and anode-HTL interface, respectively.


Importance of interface l.jpg
Importance of Interface B, H, P)

  • Interfacial phenomena represent challenging area of OLED science.

  • Carrier transport in OLED heterostructures largely injection limited.

  • Focus on hole injection attenuation and electron flux enhancement.

  • Anode-organic interface amenable to precision modification.

  • Motivated to develop nanoscopically well defined, molecule based anode-organic (HTL) interface to remove energy discontinuity.



Slide18 l.jpg

  • Characterization results from AFM, advancing aqueous contact angles, optical spectroscopy, cyclic voltammetry, XPS, UPS, and X-ray reflectivity are summarized in Table.

  • These analyses indicate, self-limiting deposition process yields conformal, largely pinhole-free, hole-transporting molecule-scale layers of subnanometer dimensions.


Oled interfacial structure charge injection relationships l.jpg
OLED Interfacial Structure-Charge Injection Relationships: angles, optical spectroscopy, cyclic voltammetry, XPS, UPS, and X-ray reflectivity are summarized in Table.

  • Responses of OLEDs having structure ITO/(SAM)/NPB/AlQ:1% DIQA/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/Li/AgMg. (A) Current density vs voltage. (B) Luminance vs voltage.


Hydrocarbon monolayers contrasts with conventional htls l.jpg
Hydrocarbon Monolayers: Contrasts with Conventional HTLs angles, optical spectroscopy, cyclic voltammetry, XPS, UPS, and X-ray reflectivity are summarized in Table.

  • ITO/n-butylsiloxane SAM/Alq OLED exhibit luminance and efficiency comparable to TAASi3 and TPDSi2 SAM based devices.

  • Alkyl based interlayers, thinner or thicker than C4 yield diminished performance.


Triarylamine functionalized anodes in polymer light emitting diodes l.jpg
Triarylamine-Functionalized Anodes in Polymer Light-Emitting Diodes

  • Triarylamine SAMs are transparent in the visible region while also offering enhanced hole injection.

  • Fabricate blue PLED based on PFO.

  • Maximum ext. q.e. and luminance ~ 40% and 3X greater for SAM vs PEDOT-PSS.

PLED devices: ITO/SAM or HTL/PFO/Ca/AL


Slide22 l.jpg


Organic field effect transistors l.jpg
Organic Field Effect Transistors times vs bare ITO.

  • The three fundamental device components are the contacts, semiconductor and the dielectric layer, typically arranged as shown in figure.

  • Need for low voltage operating, low cost manufacture gate dielectrics.


Ultrathin cross linked polymers as gate dielectrics for low voltage ofet s l.jpg
Ultrathin Cross-Linked Polymers as Gate Dielectrics for Low Voltage OFET’s

Low temp fabrication, crosslinking(insolubility), ultrathin, huge k/d ratios and low leakage current.


Dielectric patterning and capacitance l.jpg
Dielectric Patterning and Capacitance. Voltage OFET’s

  • MIM and MIS leakage and capacitance measurements carried out.

  • The current densities for CPVP-Cn and CPS-Cn films lower than for PVP and PS.

  • Ultrathin CPB’s exhibit very large capacitance values.



Slide27 l.jpg

Film pinhole assay by cyclic voltammetry using bare ITO (dotted line) and nanodielectrics III coated ITO as working electrodes (solid line).

Measurement of nanodielectric capacitance–voltage electrical characteristics at 104 Hz.


Towards n type semiconductor l.jpg
Towards N-type Semiconductor: demonstrated by cyclic voltammetry.

  • Semiconducting element in organic TFT’s: high mobility, stable and solution processable.

  • Unsubstituted,α,ω-, and β,β’- dialkyl substituted nTs and β-alkyl-substituted PTs.

  • Carrier mobilities and on/off ratios comparable to amorphous silicon.

  • Behave as p-type semiconductors; electron richness of thiophene.


Need for n type semiconductor l.jpg
Need for N-type Semiconductor demonstrated by cyclic voltammetry.

  • For full realization of the potential of organic electronics, high performance e- transporting (n-type) materials needed.

  • Enable applications, e.g. bipolar transistors, p-n junction diodes and complementary circuits.

  • Varying the substitution on thiophene backbone modulates the “band gap”.


Perfluoroalkyl substituted oligothiophenes l.jpg
Perfluoroalkyl substituted oligothiophenes demonstrated by cyclic voltammetry.

  • First compound: DFH-6T in 2000.

  • Intensive research towards understanding chemical, structural and physical properties as well as solid-state characteristics of five homologous series of thiophene based compounds.


Optical properties l.jpg
Optical properties demonstrated by cyclic voltammetry.

  • Chemical substitution has minor, but core conjugation length has marked effect.

  • Increasing number of thiophene rings and fluorocarbon substitution increase solution q.y.

  • Lower q.y. when substituents at lateral positions.

  • All oligothiophenes are conformationally more rigid in the e.s.


Electrochemistry l.jpg
Electrochemistry demonstrated by cyclic voltammetry.


Electrochemistry33 l.jpg
Electrochemistry demonstrated by cyclic voltammetry.

  • Stability of ox and red species increase with core length and substituents at end.

  • As core size increase ox and red parameters move to less +ve and –ve values; progressive reduction of electrochemical band gap.

  • ΔE1/2 value decrease with increasing core length.


Field effect transistors l.jpg
Field Effect Transistors demonstrated by cyclic voltammetry.


Field effect transistors35 l.jpg
Field Effect Transistors demonstrated by cyclic voltammetry.

  • All of the semiconductors investigated are FET-active, independent of the chemical substitution, regiochemistry, and core dimension.

  • All fluorocarbonsubstituted systems functionalized at the terminal thiophene units (1 and 2) are n-type semiconductors, in contrast to the uniformly p-type activity exhibited by the remaining systems 3-5.

  • Principal factors governing FET activity characteristics are related to the intrinsic positions of the molecular/solid-state orbitals/bands with respect to charge injection and transport.


Slide36 l.jpg

  • Electron-withdrawing strength of the perfluoroalkyl substituents is sufficient to lower both the fluorinated-nT HOMO and the LUMO energies such that electron injection and transport becomes, in the majority of cases, more favorable than hole injection and transport.


Conclusion l.jpg
Conclusion: substituents is sufficient to lower both the fluorinated-nT HOMO and the LUMO energies such that electron injection and transport becomes, in the majority of cases, more favorable than hole injection and transport.

Molecular Electronics

  • OLEDs:Triarylamine based interlayers enhance HTL adhesion and afford greater hole injection fluence, higher luminance, greater external quantum efficiency and reduced turn-on voltage.

  • Gate Dielectrics:Robust insoluble siloxane cross-linked polymeric films exhibited high capacitance and low leakage.

  • N-type Semiconductors:

    Perfluorinated thiophenes were investigated and regiochemistry, core length was found to affect OFET performance.


References l.jpg
References: substituents is sufficient to lower both the fluorinated-nT HOMO and the LUMO energies such that electron injection and transport becomes, in the majority of cases, more favorable than hole injection and transport.

Organometallics:

Hong, S.; Marks, T. J. Acc. Chem. Res.2004, 37, 673-686.

Molecular Electronics

Veinot, J. G. C.; Marks, T. J. Acc. Chem. Res.2004, 38, 632-643.

Facchetti, A.; Yoon, M.; Marks, T. J. Adv. Mater.2005, 17, 1705-1725.

Facchetti, A.; Yoon, M.; Stern, C. L.; Hutchison, G. R.; Ratner, M. A.; Marks, T. J. J. Am. Chem. Soc2004, 126, 13480-13501.

Facchetti, A.; Yoon, M.; Stern, C. L.; Hutchison, G. R.; Ratner, M. A.; Marks, T. J. J. Am. Chem. Soc2004, 126, 13859-13874.