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At least 235 records · Page 13

Photo-doping of spiro-OMeTAD for highly stable and efficient perovskite solar cells

A widely used component of high-efficiency perovskite solar cells (PSCs) is the molecular hole-transport material (HTM) spiro-OMeTAD. This organic solid needs to be p-doped to acquire sufficient hole conductivity. However, the conventional doping method using LiTFSI in the air is slow, sensitive to the environment, and may lead to the deterioration of the PSCs by unintended oxidation or dopant migration. It is thus highly desirable to develop fast doping approaches that avoid exposing the PSC to ambient air and easy-to-move dopant ions. Here, we report here that light absorption by spiro-OMeTAD itself triggers redox photochemistry that has so far been ignored. Strikingly, we found that Y(III) or La(III)-tBP complexes catalyze the symmetry-breaking charge separation of photo-excited spiro-OMeTAD, resulting in the efficient p-doping of the HTM. Using this photo-redox process, we realize PSCs with superior stability over cells using conventional doping that show no degradation under continuous illumination over 1,000 h.

14 SOLAR ENERGY↗

Electron doping of NdNiO 3 thin films using dual chamber CaH 2 annealing

Hydrogen donor doping has been exploited as a strategy to manipulate the electronic structure and electrical properties of functional oxide systems. Especially, the development of synthetic methods to achieve electron doping of perovskite rare-earth nickelate thin films utilizing interstitial hydrogen is highly desirable considering the rich electronic phase diagram hosting several functional properties. Here, in this work, we present the hydrogenation of NdNiO 3 (NNO) thin films using CaH 2 annealing and the resulting giant modulation of electrical resistivity in hydrogenated NNO (H–NNO) thin films. Magnetron sputtering was employed to deposit epitaxial ~60 nm-thin NNO films on single crystal LaAlO 3 (LAO) substrates. The formation of the pristine perovskite NNO phase was realized after annealing the films at 500 °C for 24 h. CaH 2 annealing of NNO thin films for time durations ranging from 1 to 6 h was performed in a vacuumed ampule with two interconnected chambers at 280 °C. The two-chamber design enables a simple and clean approach for hydrogen doping without physical contact between the powder and sample of interest. X-ray diffraction and Raman spectroscopy revealed the formation of NNO in pristine samples, and the subsequent hydrogen incorporation upon CaH 2 annealing without forming any impurity phases. The conversion of the oxidation state of Ni towards +2 upon CaH 2 annealing was probed using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. Consequently, a substantial increase in the room-temperature resistivity was observed upon CaH 2 annealing indicating the formation of a strongly correlated electronic configuration of Ni in H–NNO due to electron doping. Overall, the findings of this study highlight the versatility of CaH 2 annealing as an electron doping method to tune the electrical properties of correlated oxides at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-principles elucidation of the effects of Al-doping on Li-ion diffusion in LiCoO 2

Al-doped garnet Li 7 La 3 Zr 2 O 12 solid-electrolyte and LiCoO 2 cathode are promising choices as catholyte materials in all solid-state Li batteries, however, interdiffusion of Al is commonly evident during high-temperature processing and electrochemical cycling. Furthermore, to address the impact of Al interdiffusion on Li + transport properties in LiCoO 2 , we carried out a systematic evaluation of Al doping on Li + diffusion barriers in LiCoO 2 using first-principles based methods. Following the monovacancy diffusion mechanism, Al-doping (primarily at the Co site) is found to improve Li diffusion kinetics in the LiCoO 2 lattice due to favorable CoO 6 octahedral distortion experienced at the transition states. However, when considering the previously established dominant divacancy diffusion mechanism, slower Li diffusion is generally expected. In addition, a broad variation of Li diffusion barriers is observed upon Al doping, which suggests the system may suffer from non-uniform Li incorporation and diffusion that adversely affects its rate capacity during cycling. In summary, this work highlights, for the rational design of catholyte of all solid-state batteries, special attention may need to be paid to address the potential impact of non-intentional doping induced during processing on the overall electrochemical performance of the catholyte.

Al-doped LiCoO2↗

Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers

Molecularly doped conjugated polymers with polar side chains are an emerging class of conducting materials exhibiting enhanced and thermally stable conductivity. In this work, we study the electronic conductivity (σ) and the corresponding thermal stability of two polythiophene derivatives comprising oligoethylene glycol side chains: one having oxygen attached to the thiophene ring (poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET)) and the other having a methylene spacer between the oxygen and the thiophene ring (poly(3-(methoxyethoxyethoxymethyl)thiophene) (P3MEEMT)). Thin films were vapor-doped with fluorinated derivatives of tetracyanoquinodimethane (FnTCNQ, n = 4, 2, 1) to determine the role of dopant strength (electron affinity) in maximum achievable σ. Specifically, when vapor doping with F 4 TCNQ, P3MEET achieved a substantially higher σ of 37.1 ± 10.1 S/cm compared to a σ of 0.82 ± 0.06 S/cm for P3MEEMT. Structural characterization using a combination of X-ray and optical spectroscopy reveals that the higher degree of conformational order of polymer chains in the amorphous domain upon doping with F 4 TCNQ in P3MEET is a major contributing factor for the higher σ of P3MEET. Additionally, vapor-doped P3MEET exhibited superior thermal stability compared to P3MEEMT, highlighting that the presence of polar side chains alone does not ensure higher thermal stability. Molecular dynamics simulations indicate that the dopant–side-chain nonbond energy is lower in the P3MEET:F 4 TCNQ mixture, suggesting more favorable dopant–side-chain interaction, which is a factor in improving the thermal stability of a polymer/dopant pair. Our results reveal that additional factors such as polymer ionization energy and side-chain–dopant interaction should be taken into account for the design of thermally stable, highly conductive polymers.

36 MATERIALS SCIENCE↗

Basal Plane Doping to Activate Colloidal MoS 2 Nanosheets for Catalytic Hydrodeoxygenation of para- Cresol

The valorization of biomass into biofuels is a critical process for producing renewable fuels. Hydrodeoxygenation (HDO), particularly over doped molybdenum disulfide (MoS 2 ), a transition metal dichalcogenide (TMD) material, is a common representative catalytic reaction system for converting biomass-derived materials into useful hydrocarbons. However, the location and role of dopants, such as Co, in HDO is not fully understood. The effects of dopant location and oxidation state are often precluded by inhomogeneity in the ensemble properties of nanosheet size and dopant dispersion, as well as difficulty in observing the behavior of atomic site behavior directly. Using a colloidal approach to synthesize cobalt-doped MoS 2 nanosheets with controlled dopant concentration, combined with X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, we determine that basal plane doped Co (25% Co:Mo mole ratio) shows peak catalytic activity in HDO of para-cresol, a model biomass-derived compound, and that basal Co sites are demonstrably more active than edge sites. By observing these doping effects in MoS 2 catalysts for HDO, we can further optimize not only the production of carbon-neutral fuels but also direct the tailoring of doped TMD catalysts toward their intended applications.

36 MATERIALS SCIENCE↗

Pressure-Modulated Energy Transfer Dynamics in Mn 2+ -Doped CdS/ZnS Core/Shell Quantum Dots

Transition metal doping in semiconductor quantum dots (QDs) significantly impacts their optical properties, thus expanding the range of their potential optoelectronic applications. This study investigates the pressure-dependent energy transfer dynamics in Mn 2+ -doped CdS/ZnS core/shell QDs, focusing on how external hydrostatic pressure modulates these dynamics and optical properties. By synthesizing Mn 2+ -doped QDs with varying Mn 2+ doping concentrations, we explore the effects of the pressure on photoluminescence (PL) spectra and energy transfer efficiency. Our study reveals that increasing pressure induces a blueshift in the QD host bandgap PL and a redshift in the Mn 2+ dopant PL. The pressure-induced shifts highlight a unique modulation mechanism where the energy transfer efficiency decreases with pressure due to reduced wave function overlap between host excitons and Mn 2+ dopants. Detailed analysis of the PL quantum yields and energy transfer rate constants provides insights into these dynamics, suggesting that the pressure can effectively and reversibly regulate the energy transfer efficiencies and rates. In conclusion, these results have implications for developing pressure-sensitive configurable devices and exploring pressure-induced phenomena in doped nanomaterials.

36 MATERIALS SCIENCE↗

Influence of gadolinium doping on structural, optical, and electronic properties of polymeric graphitic carbon nitride

Polymeric graphitic carbon nitride (gCN) materials have received great attention in the fields of photo and electrocatalysis due to their distinct properties in metal-free systems with high physicochemical stability. Nevertheless, the activity of undoped gCN is limited due to its relatively low specific surface area, low conductivity, and poor dispersibility. Doping Gd atoms in a gCN matrix is an efficient strategy to fine-tune its catalytic activity and its electronic structure. Herein, the influence of various wt% of gadolinium (Gd) doped in melon-type carbon nitride was systematically investigated. Gadolinium-doped graphitic carbon nitride (GdgCN) was synthesized by adding gadolinium nitrate to dicyandiamide during polymerization. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the crystallinity and the morphological properties are influenced by the % of Gd doping. Furthermore, X-ray photoelectron spectroscopy (XPS) studies revealed that the gadolinium ions bonded with nitrogen atoms. Complementary density functional theory (DFT) calculations illustrate possible bonding configurations of Gd ions both in bulk material and on ultrathin melon layers and provide evidence for the corresponding bandgap modifications induced by gadolinium doping.

36 MATERIALS SCIENCE↗

Extrinsic n-type doping of Cd 3 As 2 thin films

Cd 3 As 2 provides an excellent platform for studying the physics of three-dimensional Dirac semimetals due to its stability as well as its compatibility with thin film growth. Crystals made using both bulk and thin film synthesis are unintentionally doped n-type, and other than introducing Zn to reduce the carrier concentration, no efforts have been reported to alter this intrinsic doping without major changes to the band structure. Here, group VI elements Te and Se are introduced during epitaxy to increase the electron concentration of the films. Starting from an unintentionally doped electron concentration of 1–2 × 10 17 cm -3 , concentrations of up to 3 × 10 18 cm -3 are achieved. Analysis of Shubnikov–de Haas oscillations reveals good agreement in calculated effective mass and Fermi velocity of highly doped films with unintentionally doped single crystals with similar electron concentrations. The density functional theory is also performed to study the effects of group VI substitutions and confirms no strong perturbations in the electronic structure. This work ultimately demonstrates tunability in the carrier concentration using extrinsic dopants without substantial changes in the band structure, allowing for intentional design of Fermi-level position for device applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Low-efficiency-droop c -plane InGaN/GaN light-emitting diodes through the use of thick single quantum wells and doped barriers

Efficiency droop at high current densities is a problem for InGaN-based light-emitting diodes (LEDs), especially for conventional c-plane devices. The large internal electric fields in c-plane quantum wells (QWs) lead to an increase in the active region carrier density (n), causing the electrical efficiency droop onset to occur at low current densities. Here, we present an approach to reduce the internal electric fields (Eint) in c-plane QWs by placing doped p-type and n-type GaN barriers close to the QW. The reduced Eint also allows a thick QW active region design, which helps to lower n to further reduce the droop. The concept of using doped barriers to control Eint is explained using theory and device simulations. Following that, multiple series of thick single QW (SQW) LEDs were grown and characterized. Key parameters in the epitaxial design such as the doping levels and the relative position of the doped barriers were systematically studied and optimized. In conclusion, by using optimized doped barriers and a thick SQW, c-plane LEDs with a low-efficiency droop of 14% at 300 A/cm2 [with respect to the peak external quantum efficiency (EQE)] and a high peak EQE of 49% were demonstrated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Reaction mechanisms for electrical doping of organic semiconductors using complex dopants

Electrical doping of organic semiconductors (OSCs) can be achieved using simple one-electron reductants and oxidants as n- and p-dopants, respectively, but for such dopants, increased doping strength is accompanied by increased sensitivity to ambient moisture and/or oxygen. “Indirect” or “complex” dopants—defined here as those that generate OSC radical cations or anions via pathways more complex than a single simple electron transfer, i.e., by multistep reactions—represent a means of circumventing this problem. Further, this review highlights the importance of understanding the reaction mechanisms by which such dopants operate for: (i) ensuring a researcher knows the composition of a doped material; (ii) predicting the thermodynamic feasibility of achieving doping with related dopant:OSC combinations; and (iii) predicting whether thermodynamically feasible doping reactions are likely to be rapid or slow, or to require subsequent activation. The mechanistic information available to date for some of the wide variety of complex n- and p-dopants that have been reported is then reviewed, emphasizing that in many cases our knowledge is far from complete.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational Fermi Level Engineering and Doping-Type Conversion of Ga2O3 Via Three-Step Processing

Ga2O3 is being actively explored for power electronics, and other applications due to its ultra- wide bandgap and low projected fabrication cost of high-quality crystals. N-type doping of Ga2O3 can be achieved and tuned, but p-type doping faces fundamental obstacles. Successful engineering of Ga2O3 based devices requires critical control of doping density, Fermi level position, providing opportunities for predictive process simulation. We use first-principles defect equilibrium calculations to simulate a 3-step growth- annealing-quench protocol for hydrogen assisted Mg doping in Ga2O3, taking into account the hydrogen- oxygen-water gas phase equilibrium. We predict type conversion to a net p-type regime following O-rich annealing after growth under reducing conditions in the presence of H2. We show that there is an optimal temperature that maximizes the net acceptor density during the equilibrium annealing step for a given Mg doping level. Quenching of non-equilibrium annealed samples then results in a Fermi level EF below mid-gap down to about EV +1.5 eV, creating a significant number of uncompensated neutral MgGa0 acceptors. This type converted Ga2O3 can create significant built-in field in a p-n junction with an adjoining n-type material and could enable vertical MOSFETs.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗

Stable High‐Conductivity Ethylenedioxythiophene Polymers via Borane‐Adduct Doping

Efficient doping of polymer semiconductors is required for high conductivity and efficient thermoelectric performance. Lewis acids, e.g., B(C 6 F 5 ) 3 , have been widely employed as dopants, but the mechanism is not fully understood. 1:1 “Wheland type” or zwitterionic complexes of B(C 6 F 5 ) 3 are 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(C 6 F 5 ) 3 are 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(C 6 F 5 ) 3 , serving as the oxidant. It is highly probable that certain repeat units/segments form adduct structures in p -type conjugated polymers which act as intermediates for conjugated polymer doping. Electronic and optical properties are consistent with the increase in hole-donating ability of polymers with their cumulative donor strengths. The doped film of polymer (DPP(EDOT) 2 -(EDOT) 2 ) exhibits exceptionally good thermal and air-storage stability. The highest conductivities, ≈300 and ≈200 S cm -1 , are achieved for DPP(EDOT) 2 -(EDOT) 2 doped with B(C 6 F 5 ) 3 and its Wheland complexes.

36 MATERIALS SCIENCE↗

Controlled Dedoping and Redoping of N‐Doped Poly(benzodifurandione) (n‐PBDF)

Abstract The doping levels of conjugated polymers significantly influence their conductivity, energetics, and optical properties. Recently, a highly conductive n‐doped polymer called poly (3,7‐dihydrobenzo[1,2‐b:4,5‐b′]difuran‐2,6‐dione) (poly(benzodifurandione), n‐PBDF) is discovered, opening new possibilities for n‐type conducting polymers in printed electronics and other fields. Controlling the doping level of n‐PBDF is of great interest due to its wide range of potential applications. Here controlled dedoping and redoping of n‐PBDF is reported and a mechanistic understating of such a process is provided. Dedoping occurs through electron transfer and proton capture, wherein the ionic dopants, tris(4‐bromophenyl)ammoniumyl hexachloroantimonate (Magic Blue), exhibit efficient proton capture ability and stronger interaction with n‐PBDF, resulting in high dedoping efficiency. Moreover, chemically dedoped PBDF can be redoped using various proton‐coupled electron transfer agents. By manipulating the doping levels of n‐PBDF thin films, ranging from highly doped to dedoped states, the system demonstrates controllable conductivity in five orders of magnitude, adjustable optical properties, and energetics. As a result, these characteristics demonstrate the potential applications of n‐PBDF in organic electrochemical transistors and thermoelectrics.

Chemistry↗

Scalable Substitutional Re‐Doping and its Impact on the Optical and Electronic Properties of Tungsten Diselenide

Abstract Reliable, controlled doping of 2D transition metal dichalcogenides will enable the realization of next‐generation electronic, logic‐memory, and magnetic devices based on these materials. However, to date, accurate control over dopant concentration and scalability of the process remains a challenge. Here, a systematic study of scalable in situ doping of fully coalesced 2D WSe 2 films with Re atoms via metal–organic chemical vapor deposition is reported. Dopant concentrations are uniformly distributed over the substrate surface, with precisely controlled concentrations down to <0.001% Re achieved by tuning the precursor partial pressure. Moreover, the impact of doping on morphological, chemical, optical, and electronic properties of WSe 2 is elucidated with detailed experimental and theoretical examinations, confirming that the substitutional doping of Re at the W site leads to n‐type behavior of WSe 2 . Transport characteristics of fabricated back‐gated field‐effect‐transistors are directly correlated to the dopant concentration, with degrading device performances for doping concentrations exceeding 1% of Re. The study demonstrates a viable approach to introducing true dopant‐level impurities with high precision, which can be scaled up to batch production for applications beyond digital electronics.

Kozhakhmetov, Azimkhan↗

Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers

In both chemical and electrochemical doping of organic semiconductors (OSCs), a counterion, either from the electrolyte or ionized dopant, balances the charge introduced to the OSC. Despite the large influence of this counterion on OSC optical and electronic response, there remains substantial debate on how a fundamental parameter, ion size, impacts these properties. Here, this work resolves much of this debate by accounting for two doping regimes. In the low-doping regime, the Coulomb binding energies between charge carriers on the OSC and the counterions are significant, and larger counterions lead to decreased Coulomb interactions, more delocalized charge carriers, and higher electrical conductivities. In the high-doping regime, the Coulomb binding energies become negligible due to the increased dielectric constant of the films and a smoothing of the energy landscape; thereby, the electrical conductivities depend primarily on the extent of morphological disorder in the OSC. Moreover, in regioregular poly(3-hexylthiophene), rr-P3HT, smaller counterions lead to greater bipolaron concentrations in the low-doping regime due to the increased Coulomb interactions. Emphasizing the impact of the counterion size, it is shown that larger counterions can lead to increased thermoelectric power factors for rr-P3HT.

36 MATERIALS SCIENCE↗

Controllable Thin‐Film Approaches for Doping and Alloying Transition Metal Dichalcogenides Monolayers

Abstract Two‐dimensional (2D) transition metal dichalcogenides (TMDs) exhibit exciting properties and versatile material chemistry that are promising for device miniaturization, energy, quantum information science, and optoelectronics. Their outstanding structural stability permits the introduction of various foreign dopants that can modulate their optical and electronic properties and induce phase transitions, thereby adding new functionalities such as magnetism, ferroelectricity, and quantum states. To accelerate their technological readiness, it is essential to develop controllable synthesis and processing techniques to precisely engineer the compositions and phases of 2D TMDs. While most reviews emphasize properties and applications of doped TMDs, here, recent progress on thin‐film synthesis and processing techniques that show excellent controllability for substitutional doping of 2D TMDs are reported. These techniques are categorized into bottom–up methods that grow doped samples on substrates directly and top–down methods that use energetic sources to implant dopants into existing 2D crystals. The doped and alloyed variants from Group VI TMDs will be at the center of technical discussions, as they are expected to play essential roles in next‐generation optoelectronic applications. Theoretical backgrounds based on first principles calculations will precede the technical discussions to help the reader understand each element's likelihood of substitutional doping and the expected impact on the material properties.

36 MATERIALS SCIENCE↗

Pressure‐Dependent “Insulator–Metal–Insulator” Behavior in Sr‐Doped La 3 Ni 2 O 7

Abstract Recently, superconductivity at high temperatures is observed in bulk La 3 Ni 2 O 7−δ under high pressure. However, the attainment of high‐purity La 3 Ni 2 O 7−δ single crystals remains a formidable challenge. Here, the crystal structure and physical properties of single crystals of Sr‐doped La 3 Ni 2 O 7 synthesized at high pressure (20 GPa) and high temperature (1400 °C) are reported. Through single crystal X‐ray diffraction, it is shown that high‐pressure‐synthesized paramagnetic Sr‐doped La 3 Ni 2 O 7 crystallizes in an orthorhombic structure with Ni─O─Ni bond angles of 173.4(2)° out‐of‐plane and 175.0(2)°and 176.7(2)°in plane. The substitution of Sr alters in band filling and the ratio of Ni 2+ /Ni 3+ in Sr‐doped La 3 Ni 2 O 7 , aligning them with those of “La 3 Ni 2 O 7.05” , thereby leading to significant modifications in properties under high pressure relative to the unsubstituted parent phase. At ambient pressure, Sr‐doped La 3 Ni 2 O 7 exhibits insulating properties, and the conductivity increases as pressure goes up to 10 GPa. However, upon further increasing pressure beyond 10.7 GPa, Sr‐doped La 3 Ni 2 O 7 transits back from a metal‐like behavior to an insulator. The insulator–metal–insulator trend under high pressure dramatically differs from the behavior of the parent compound La 3 Ni 2 O 7−δ , despite their similar behavior in the low‐pressure regime. These experimental results underscore the considerable challenge in achieving superconductivity in nickelates.

36 MATERIALS SCIENCE↗

N‐Doping Effects On Electrocatalytic Water Splitting of Non‐Noble High‐Entropy Alloy Nanoparticles Prepared by Inert Gas Condensation

Abstract The unique catalytic activities of high‐entropy alloys (HEAs) emerge from the complex interaction among different elements in a single‐phase solid solution. As a “green” nanofabrication technique, inert gas condensation (IGC) combined with laser source opens up a highly efficient avenue to develop HEA nanoparticles (NPs) for catalysis and energy storage. In this work, the novel N‐doped non‐noble HEA NPs are designed and successfully prepared by IGC. The N‐doping effects of HEA NPs on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are systematically investigated. The results show that N‐doping is conducive to improving the OER, but unfavorable for HER activity. The FeCoNiCrN NPs achieve an overpotential of 269.7 mV for OER at a current density of 10 mA cm −2 in 1.0 M KOH solution, which is among the best reported values for non‐noble HEA catalysts. The effects of the differences in electronegativity, ionization energy and electron affinity energy among mixed elements in N‐doped HEAs are discussed as inducing electron transfer efficiency. Combined with X‐ray photoelectron spectroscopy and the extended X‐ray absorption fine structure analysis, an element‐design strategy in N‐doped HEAs electrocatalysts is proposed to improve the intrinsic activity and ameliorate water splitting performance.

Chemistry↗