Efficient doping of polymer semiconductors is required for high conductivity and efficient thermoelectric performance. Lewis acids, e.g., B(C6F5)3, have been widely employed as dopants, but the mechanism is not fully understood. 1:1 “Wheland type” or zwitterionic complexes of B(C6F5)3are created with small conjugated molecules 3,6‐bis(5‐(7‐(5‐methylthiophen‐2‐yl)‐2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)thiophen‐2‐yl)‐2,5‐dioctyl‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione [oligo_DPP(EDOT)2] and 3,6‐bis(5''‐methyl‐[2,2':5',2''‐terthiophen]‐5‐yl)‐2,5‐dioctyl‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione [oligo_DPP(Th)2]. Using a wide variety of experimental and computational approaches, the doping ability of these Wheland Complexes with B(C6F5)3are characterized for five novel diketopyrrolopyrrole‐ethylenedioxythiophene (DPP‐EDOT)‐based conjugated polymers. The electrical properties are a strong function of the specific conjugated molecule constituting the adduct, rather than acidic protons generated via hydrolysis of B(C6F5)3, serving as the oxidant. It is highly probable that certain repeat units/segments form adduct structures in
Diamond is a wide-bandgap semiconductor possessing exceptional physical and chemical properties with the potential to miniaturize high-power electronics. Whereas boron-doped diamond (BDD) is a well-known p-type semiconductor, fabrication of practical diamond-based electronic devices awaits development of an effective n-type dopant with satisfactory electrical properties. Here we report the synthesis of n-type diamond, containing boron (B) and oxygen (O) complex defects. We obtain high carrier concentration (∼0.778 × 1021cm−3) several orders of magnitude greater than previously obtained with sulfur or phosphorous, accompanied by high electrical conductivity. In high-pressure high-temperature (HPHT) boron-doped diamond single crystal we formed a boron-rich layer ∼1–1.5 μm thick in the {111} surface containing up to 1.4 atomic % B. We show that under certain HPHT conditions the boron dopants combine with oxygen defects to form B–O complexes that can be tuned by controlling the experimental parameters for diamond crystallization, thus giving rise to n-type conduction. First-principles calculations indicate that B3O and B4O complexes with low formation energies exhibit shallow donor levels, elucidating the mechanism of the n-type semiconducting behavior.
more » « less- NSF-PAR ID:
- 10091548
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 116
- Issue:
- 16
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- p. 7703-7711
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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