Polyanionic, Alkylthiosulfate-Based Thiol Precursors for Conjugated Polymer Self-Assembly onto Gold and Silver

Kraft, Mario; Adamczyk, Sylwia; Polywka, Andreas; Zilberberg, Kirill; Weijtens, Christ H. L.; Meyer, Jens; Görrn, Patrick; Riedl, Thomas; Scherf, Ullrich

doi:10.1021/am5025148

Cited by 17 publications

(15 citation statements)

References 33 publications

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“…[ 1,6 ] There have been some efforts devoted to the development of CPEs capable of hole transportation (henceforth referred to as p-type CPEs) by varying their polymeric structures, including their conjugated backbones, ionic functionalities, and functional group in alkyl side chains. [ 8,10 ] However, such simple structural modifi cation may not be effective in modulating the strengths and directions of dipoles, which are determining factors in modifying the WFs of CPE-covered metal electrodes. [ 9,11 ] Here, we report the preparation of a collection of unprecedented p-type CPEs synthesized via the self-doping of conventional n-type CPEs.…”

Section: Doi: 101002/aenm201401653mentioning

confidence: 99%

Broad Work‐Function Tunability of p‐Type Conjugated Polyelectrolytes for Efficient Organic Solar Cells

Lee

Jeong

et al. 2014

Advanced Energy Materials

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(HTLs). Through facile oxidation of n-type CPEs using oxidants (X 2 S 2 O 8 , where X = K, NH 4 , and Na), self-doped p-type CPEs are generated with radical cations (i.e., polarons) in their backbones, inducing dramatic changes in the directions and strengths of dipoles at the metal anodes/semiconductor interfaces. These p-type CPEs systematically shift the effective WFs of indium tin oxide (ITO) from 4.80 to 5.04-5.35 eV according to differing degrees of the doping concentration and effectively act as HTL materials in organic solar cells. Substantial changes in power conversion effi ciency (PCE) and device lifetimes are demonstrated with increases in the doping concentration.Our research begins with the identifi cation of an n-type CPE as a doping counterpart and then employs various oxidants with different oxidative potentials to control the doping concentration of the resulting p-type CPEs. Extensive research has shown that the use of anionic PFP [poly(9,9-bis(4′-sulfonatobutyl) fl uorene-alt -co -1,4-phenylene)] as an electron-transport layer (ETL) in organic electronic devices provides excellent device performance, [ 1 ] although PFP has never been demonstrated as an HTL. It should be noted that "anionic" CPEs are essential for this strategy because their anionic functionality (here, SO 3 − ) is able to stabilize radical cations in self-doped conducting polymers. [12][13][14] The proposed structure after the oxidative doping of n-type PFP ( Figure 1 ) suggests that the SO 3 − functional group might couple with the oxidized backbone, in the place of the Na + cation, during the oxidation process. In principle, not all repeating units would be oxidized, as the doping concentration is controlled by the oxidative strength of the oxidants employed.

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Section: Doi: 101002/aenm201401653mentioning

confidence: 99%

Broad Work‐Function Tunability of p‐Type Conjugated Polyelectrolytes for Efficient Organic Solar Cells

Lee

Jeong

et al. 2014

Advanced Energy Materials

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“…[ 5,8,[18][19][20][21] Furthermore, CPEs offer several advantages over other interlayer materials: neutrality (pH ≈ 7), which enhances the stability of the devices during operation; solution-processability, which provides their compatibility with roll-to-roll printing; a room-temperature process, which is necessary for plastic electronics; and property-controllability through a design of their chemical structure, such as π-conjugated backbones and ionic groups, [ 22,23 ] which ensures their boundless potential as interlayers for the fi ne modulation of the WFs of metal electrodes in various applications. [ 8 ] However, all CPEs developed thus far can only decrease the WFs of metals, and they have been utilized only as a cathode interlayer.…”

mentioning

confidence: 99%

Radical Cation–Anion Coupling‐Induced Work Function Tunability in Anionic Conjugated Polyelectrolytes

Lee

Jeong

et al. 2015

Advanced Energy Materials

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edioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS), [ 9 ] sol-gel-processed metal oxides, [ 10 ] self-assembled monolayers, [ 11 ] quantum dots, [ 12 ] 2D nanomaterials, [ 13,14 ] ionic compounds, [ 15,16 ] and oxygen-plasma treatment. [ 17 ] However, those methods suffer from various drawbacks, such as an acidic nature, a high processing temperature, poor stability in air, or processing that is incompatible with various printing fabrication techniques (i.e., the roll-to-roll printing method), which need to be overcome for their successful application to organic electronics.Conjugated polyelectrolytes (CPEs), π-conjugated polymers with ionic groups on the side chains, have been used to effectively reduce the energy barrier between the metal electrode and the organic active layer through the development of an electric dipole layer and a shift in the vacuum levels of the adjacent active layers. [ 5,8,[18][19][20][21] Furthermore, CPEs offer several advantages over other interlayer materials: neutrality (pH ≈ 7), which enhances the stability of the devices during operation; solution-processability, which provides their compatibility with roll-to-roll printing; a room-temperature process, which is necessary for plastic electronics; and property-controllability through a design of their chemical structure, such as π-conjugated backbones and ionic groups, [ 22,23 ] which ensures their boundless potential as interlayers for the fi ne modulation of the WFs of metal electrodes in various applications. [ 8 ] However, all CPEs developed thus far can only decrease the WFs of metals, and they have been utilized only as a cathode interlayer. [ 18 ] Recently, a new class of CPEs (henceforth referred to as p-type CPEs) for anodes was developed through a facile oxidative doping of pristine anionic CPEs (henceforth referred to as n-type CPEs) by Bazan's group in University of California, Santa Barbara (UCSB) and also our group in Gwangju Institute of Science and Technology (GIST). [ 24,25 ] The p-type CPEs show a broad WF tunability for various metal electrodes by forming self-aligned electric dipoles with a reversed direction to those of n-type CPEs, [ 25 ] and they exhibit superior hole-extracting ability in polymer solar cells (PSCs) or small molecule solar cells according to previous works. [25][26][27] However, in spite of the successful incorporation of p-type CPEs into various organic electronics as effi cient interlayers, the fundamental mechanism for how the direction and strength of electric dipoles are reversed By coating conjugated polyelectrolytes (CPEs) on metals, the work function (WF) of metals can be tuned by electric dipoles formed through the selfassembly of cation-anion pairs on the side chains of CPEs. Recently, it has been reported that a pertinent oxidative doping of anionic CPEs results in a reversed direction in the net electric dipoles, thereby yielding opposite WF tunability compared with pristine CPEs. However, the fundamental mechanism of this reversed WF tunability is not clearly understood. Here, t...

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“…The ID/IG decreases to 1.45 for the Au NPs@HS-G-PMS, possibly as a result of the Au NPs growth at defective regions of the HS-G-PMS surface. 20 The microstructure and morphology of the hybrids are characterized by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SERS were obtained via an electromagnetic enhancement (excitation of localized surface plasmons involving a physical interaction) or chemical enhancement (formation of chargetransfer complexes involving chemical interaction) with enhancement factors of ~ 10 12 and ~10 to 100, respectively.…”

Section: Characterizationmentioning

confidence: 99%

Gold nanoparticles decorated on a graphene-periodic mesoporous silica sandwich nanocomposite as a highly efficient and recyclable heterogeneous catalyst for catalytic applications

2015

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ARTICLE This journal isThe ultra-small Au nanoparticles (Au NPs) immobilized HS-functionalized sandwich-like periodic mesoporous silica (PMS) coated graphene (G) to form a novel nanocomposite catalyst Au NPs@HS-G-PMS. The synthesized Au NPs@HS-G-PMS nanocatalyst exhibited excellent catalytic activity on the three kinds of organic reactions. The reduction of 4-nitrophenol by sodium borohydride, the Suzuki-Miyaura cross coupling reaction of aryl halides with phenyl boronic acid and three coupling reaction of aldehyde, alkyne, and secondary amine (A 3 -coupling) in water were successfully done. Most importantly, the catalyst could be used repetitively more than six times without significant deactivation.

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Polyanionic, Alkylthiosulfate-Based Thiol Precursors for Conjugated Polymer Self-Assembly onto Gold and Silver

Cited by 17 publications

References 33 publications

Broad Work‐Function Tunability of p‐Type Conjugated Polyelectrolytes for Efficient Organic Solar Cells

Broad Work‐Function Tunability of p‐Type Conjugated Polyelectrolytes for Efficient Organic Solar Cells

Radical Cation–Anion Coupling‐Induced Work Function Tunability in Anionic Conjugated Polyelectrolytes

Gold nanoparticles decorated on a graphene-periodic mesoporous silica sandwich nanocomposite as a highly efficient and recyclable heterogeneous catalyst for catalytic applications

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