Thin films of amorphous small molecule semiconductors are widely used in organic light emitting displays and have promising applications in solar cells and thermoelectric devices. Adding dopants increases the conductivity of organic semiconductors, but high concentrations of dopants can disrupt their structural ordering, alter the shape of the electronic density of states in the material, and increase the effects of Coulomb interactions on charge transport. Electrical doping of the solution processable hole-transport material 2,2′,7,7′-tetrakis[ N , N -di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) was studied with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) as a p-type dopant. Infiltration of F 4 TCNQ from the vapor phase into films of spiro-OMeTAD provided a route to highly doped films with up to 39 ± 2 mol% doping. Structural characterization confirmed that the films remain amorphous even at the highest doping levels with no apparent phase separation. We quantitatively determined the carrier concentration using UV-Vis spectroscopy to interpret the evolution of the electrical conductivity. Over the range of carrier concentrations (10 19 –10 20 1 cm −3 ), the electrical conductivity increased no more than linearly with carrier concentration, while the thermopower had a small increase with carrier concentration. The trends in conductivity and thermopower were related to the unique electronic structure of spiro-OMeTAD, which is able to support two carriers per molecule. Temperature-dependent conductivity measurements were used to further analyze the transport mechanism.
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Revealing the intrinsic transport properties of antiperovskite Sr3SnO thin films
A topologically non-trivial band structure and reports of superconductivity have motivated significant investigation into the transport properties of the antiperovskite oxide Sr3SnO. Phase-pure films of Sr3SnO can be grown by molecular beam epitaxy, but they do not have the required extremely high hole-doping densities (>1 × 1021 cm−3) for which superconductivity has been observed in bulk materials. To date, high hole-doping densities have been achieved via inducing strontium deficiency, which inevitably results in impurity phases. Here, we show that indium acts as an effective hole dopant in Sr3SnO and can be used to achieve high hole doping densities in stoichiometric films. Films with carrier densities as high as 1.5 × 1021 cm−3 remain non-superconducting. We, therefore, suggest that Sr3SnO is probably not an intrinsic superconductor. A second question addressed in this work is the measurement of the intrinsic electrical transport properties of Sr3SnO, given its rapid degradation in air. We show that even in inert atmospheres, reducing the time needed for establishing electrical contacts and protecting the Sr3SnO film result in improved electrical properties. We demonstrate low carrier density films (4 × 1018 cm−3) with carrier mobilities of 400 cm2 V−1 s−1 at 10 K.
more » « less- NSF-PAR ID:
- 10439947
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- Applied Physics Letters
- Volume:
- 121
- Issue:
- 23
- ISSN:
- 0003-6951
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Ultra-violet light emitting diodes (UV-LEDs) and lasers based on the III-Nitride material system are very promising since they enable compact, safe, and efficient solid-state sources of UV light for a range of applications. The primary challenges for UV LEDs are related to the poor conductivity of p-AlGaN layers and the low light extraction efficiency of LED structures. Tunnel junction-based UV LEDs provide a distinct and unique pathway to eliminate several challenges associated with UV LEDs1-4. In this work, we present for the first time, a reversed-polarization (p-down) AlGaN based UV-LED utilizing bottom tunnel junction (BTJ) design. We show that compositional grading enables us to achieve the lowest reported voltage drop of 1.1 V at 20 A/cm2 among transparent AlGaN based tunnel junctions at this Al-composition. Compared to conventional LED design, a p-down structure offers lower voltage drop because the depletion barrier for both holes and electrons is lower due to polarization fields aligning with the depletion field. Furthermore, the bottom tunnel junction also allows us to use polarization grading to realize better p- and n-type doping to improve tunneling transport. The epitaxial structure of the UV-LED was grown by plasma-assisted molecular beam epitaxy (PAMBE) on metal-organic chemical vapor deposition (MOCVD)-grown n-type Al0.3Ga0.7N templates. The transparent TJ was grown using graded n++-Al0.3Ga0.7N→ n++-Al0.4Ga0.6N (Si=3×1020 cm-3) and graded p++-Al0.4Ga0.6N →p++-Al0.3Ga0.7N (Mg=1×1020 cm-3) to take advantage of induced 3D polarization charges. The high number of charges at the tunnel junction region leads to lower depletion width and efficient hole injection to the p-type layer. The UV LED active region consists of three 2.5 nm Al0.2Ga0.8N quantum wells and 7 nm Al0.3Ga0.6N quantum barriers followed by 12 nm of p- Al0.46Ga0.64N electron blocking layer (EBL). The active region was grown on top of the tunnel junction. A similar LED with p-up configuration was also grown to compare the electrical performance. The surface morphology examined by atomic force microscopy (AFM) shows smooth growth features with a surface roughness of 1.9 nm. The dendritic features on the surface are characteristic of high Si doping on the surface. The composition of each layer was extracted from the scan by high resolution x-ray diffraction (HR-XRD). The electrical characteristics of a device show a voltage drop of 4.9 V at 20 A/cm2, which corresponds to a tunnel junction voltage drop of ~ 1.1 V. This is the best lowest voltage for transparent 30% AlGaN tunnel junctions to-date and is comparable with the lowest voltage drop reported previously on non-transparent (InGaN-based) tunnel junctions at similar Al mole fraction AlGaN. On-wafer electroluminescence measurements on patterned light-emitting diodes showed single peak emission wavelength of 325 nm at 100 A/cm2 which corresponds to Al0.2Ga0.8N, confirming that efficient hole injection was achieved within the structure. The device exhibits a wavelength shift from 330 nm to 325 nm with increasing current densities from 10A/cm2 to 100A/cm2. In summary, we have demonstrated a fully transparent bottom AlGaN homojunction tunnel junction that enables p-down reversed polarization ultraviolet light emitting diodes, and has very low voltage drop at the tunnel junction. This work could enable new flexibility in the design of future III-Nitride ultraviolet LEDs and lasers.more » « less
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Abstract Semiconducting mesocrystalline bulk polymer specimens that exhibit near‐intrinsic properties using channel‐die pressing are demonstrated. A predominant edge‐on orientation is obtained for poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) throughout 2 mm‐thick/wide samples. This persistent mesocrystalline arrangement at macroscopic scales allows reliable evaluation of the electronic charge‐transport anisotropy along all three crystallographic axes, with high mobilities found along the π‐stacking. Indeed, charge‐carrier mobilities of up to 2.3 cm2V−1s−1are measured along the π‐stack, which are some of the highest mobilities reported for polymers at low charge‐carrier densities (drop‐cast films display mobilities of maximum ≈10−3cm2V−1s−1). The structural coherence also leads to an unusually well‐defined photoluminescence line‐shape characteristic of an H‐aggregate (measured from the surface perpendicular to the materials flow), rather than the typical HJ‐aggregate feature usually found for P3HT. The approach is widely applicable: to electrical conductors and materials used in n‐type devices, such as poly{[
N ,N ′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt ‐5,5′‐(2,2′‐bithiophene)} (N2200) where the mesocrystalline structure leads to high electron transport along the polymer backbones (≈1.3 cm2V−1s−1). This versatility and the broad applicability of channel‐die pressing signifies its promise as a straightforward, readily scalable method to fabricate bulk semiconducting polymer structures at macroscopic scales with properties typically accessible only by the tedious growth of single crystals. -
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It has been challenging to synthesize p-type SnOx(1≤x<2) and engineer the electrical properties such as carrier density and mobility due to the narrow processing window and the localized oxygen 2p orbitals near the valence band.
We recently reported on the processing of p-type SnOx and an oxide-based p-n heterostructures, demonstrating high on/off rectification ratio (>103), small turn-on voltage (<0.5 V), and low saturation current (~1×10-10A)1. In order to further understand the p-type oxide and engineer the properties for various electronic device applications, it is important to identify (or establish) the dominating doping and transport mechanisms. The low dopability in p-type SnOx, of which the causation is also closely related to the narrow processing window, needs to be mitigated so that the electrical properties of the material are to be adequately engineered2, 3.
Herein, we report on the multifunctional encapsulation of p-SnOxto limit the surface adsorption of oxygen and selectively permeate hydrogen into the p-SnOxchannel for thin film transistor (TFT) applications. Time-of-flight secondary ion mass spectrometry measurements identified that ultra-thin SiO2as a multifunctional encapsulation layer effectively suppressed the oxygen adsorption on the back channel surface of p-SnOxand augmented hydrogen density across the entire thickness of the channel. Encapsulated p-SnOx-based TFTs demonstrated much-enhanced channel conductance modulation in response to the gate bias applied, featuring higher on-state current and lower off-state current. The relevance between the TFT performance and the effects of oxygen suppression and hydrogen permeation is discussed in regard to the intrinsic and extrinsic doping mechanisms. These results are supported by density-functional-theory calculations.
Acknowledgement This work was supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 20011028) by KRISS. K.N. was supported by Basic Science Research Program (NRF-2021R11A1A01051246) through the NRF Korea funded by the Ministry of Education.
References Lee, D. H.; Park, H.; Clevenger, M.; Kim, H.; Kim, C. S.; Liu, M.; Kim, G.; Song, H. W.; No, K.; Kim, S. Y.; Ko, D.-K.; Lucietto, A.; Park, H.; Lee, S., High-Performance Oxide-Based p–n Heterojunctions Integrating p-SnOx and n-InGaZnO.
ACS Applied Materials & Interfaces 2021, 13 (46), 55676-55686.Hautier, G.; Miglio, A.; Ceder, G.; Rignanese, G.-M.; Gonze, X., Identification and design principles of low hole effective mass p-type transparent conducting oxides.
Nat Commun 2013, 4 .Yim, K.; Youn, Y.; Lee, M.; Yoo, D.; Lee, J.; Cho, S. H.; Han, S., Computational discovery of p-type transparent oxide semiconductors using hydrogen descriptor.
npj Computational Materials 2018, 4 (1), 17.Figure 1
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In materials with broken time-reversal symmetry, the Berry curvature acts as a recip- rocal space magnetic field on the conduction electrons and is a significant contribution to the magnetotransport properties, including the intrinsic anomalous Hall effect. Here, we report neutron diffraction, transport, and magnetization measurements of thin films of doped EuTiO3, an itinerant magnetic material, as a function of carrier density and magnetic field. These films are itinerant antiferromagnets at all doping concentrations. At low carrier densities, the magnetoresistance indicates a metamag- netic transition, which is absent at high carrier densities (>6 × 1020 cm-3). Strikingly, the crossover coincides with a sign change in the spontaneous Hall effects, indicating a sign change in the Berry curvature. We discuss the results in the context of the band structure topology and its coupling to the magnetic texture.more » « less
