Doped Semiconductors Research Articles

Simultaneous study of acoustic and optic phonon scattering of electrons and holes in undoped GaAs/AlxGa1−xAs heterostructures

The study of phonon coupling in doped semiconductors via electrical transport measurements is challenging due to unwanted temperature-induced effects such as dopant ionization and parallel conduction. Here, we study phonon scattering in 2D electrons and holes in the 1.6–92.5 K range without the use of extrinsic doping, where both acoustic and longitudinal optic (LO) phonons come into effect. We use undoped GaAs/AlxGa1−xAs heterostructures and examine the temperature dependence of the sample resistivity, extracting phonon coupling constants and the LO activation energy. Our results are consistent with results obtained through approaches other than transport measurements and highlight the benefit of this approach for studying electron–phonon and hole–phonon coupling.

Electrophilic-Attack Doped Organic Field-Effect Transistors for Ultrasensitive and Selective Hydrogen Sulfide Detection.

Doping of organic semiconductors (OSCs) has been developed as an effective means of modulating the density and transfer efficiency of charge carriers; however, realization of effective doping to tailor the chemical sensing performance of OSC-based sensors still remains not explored extensively. In addition, the application of OSCs in chemical sensors is usually limited by the poor stability and low selectivity. Herein, flexible donor-acceptor copolymer-based organic field-effect transistor (OFET) chemical sensors are designed via an electrophilic attack doping strategy. The p-dopant trityl tetrakis(pentafluorophenyl) borate (TrTPFB) can be effectively doped into the host molecular N-alkyl-diketopyrrolo-pyrroledithienylthieno[3,2-b]thiophene (DPPDTT). It is simple to alter the doping efficiency and film thickness (ca. 5.5-17.7 nm) by adjusting the proportion and concentration of guest-host molecules, which endows facile carrier mobility and enhanced sensing sensitivity modulation toward reducing gases at room temperature. Particularly, 1.0 mol% TrTPFB-doped DPPDTT achieved the highest response to H2S gas, including ultralow detection concentration (0.5 ppb), excellent selectivity, high humidity stability, and long-term storage stability. This work can provide a new strategy for the potential applications of the organic electronic sensing devices.

Precise p-type and n-type doping of two-dimensional semiconductors for monolithic integrated circuits

The controllable fabrication of patterned p-type and n-type channels with precise doping control presents a significant challenge, impeding the realization of complementary metal-oxide-semiconductor (CMOS) logic using a single van der Waals material. However, such an achievement could offer substantial benefits by enabling continued transistor scaling and unprecedented interlayer interconnect technologies. In this study, we devise a precise method for two-dimensional (2D) semiconductor substitutional doping, which allows for the production of wafer-scale 2H-MoTe2 thin films with specific p-type or n-type doping. Notably, we extend this approach to the synthesis of spatially selective doped 2H-MoTe2 thin films via a one-step growth method, facilitating the monolithic integration of p-type and n-type semiconductor channels. Leveraging this advancement, we successfully fabricate a chip-sized 2D CMOS inverter array that demonstrates excellent device performance and yield. Collectively, these findings represent a significant stride towards the practical incorporation of 2D semiconductors in very large-scale integration technology.

Influence of platinum content on semiconductor and electrochemical properties of materials based on titanium suboxides

The effect of platinum content on the surface morphology, phase composition and electrochemical properties of materials based on titanium suboxides was investigated. Titanium suboxides are formed at the stage of coating reduction under cathodic polarization, which allows the formation of a porous developed surface for electrodeposition of catalytic platinum layers. The main allotropic modification of TiOx in the studied composite materials is anatase, which contains particles of elemental titanium and platinum. The investigated materials are highly doped semiconductors with a high concentration of charge carriers. With an increase in the platinum content, an extreme dependence of the potential of flat zones is observed, which is associated with the formation of a composite material. The electrocatalytic activity was studied in the reactions of oxygen and hydrogen evolution. The overvoltage of oxygen production on platinum-containing materials is much lower than on the TiOx electrode. The slope of the linear dependence of the potential on the current density decreases with an increase in platinum content. The Tafel slope for the studied materials in the hydrogen evolution reaction was 160 mVdec–1 for coatings containing 0.25 mgcm–2 Pt; whereas it was equal to 42 and 43 mVdec–1 for electrodes with 0.5 and 2 mgcm–2 Pt, respectively.

Surface Defects Control Bulk Carrier Densities in Polycrystalline Pb-Halide Perovskites.

The (opto)electronic behavior of semiconductors depends on their (quasi-)free electronic carrier densities. These are regulated by semiconductor doping, i.e., controlled "electronic contamination". For metal halide perovskites (HaPs), the functional materials in several device types, which already challenge some of the understanding of semiconductor properties, this study shows that doping type, density and properties derived from these, are to a first approximation controlled via their surfaces. This effect, relevant to all semiconductors, and already found for some, is very evident for lead (Pb)-HaPs because of their intrinsically low electrically active bulk and surface defect densities. Volume carrier densities for most polycrystalline Pb-HaP films (<1µm grain diameter) are below those resulting from even < 0.1% of surface sites being electrically active defects. This implies and is consistent with interfacial defects controlling HaP devices in multi-layered structures with most of the action at the two HaP interfaces. Surface and interface passivation effects on bulk electrical properties are relevant to all semiconductors and are crucial for developing those used today. However, because bulk dopant introduction in HaPs at controlled ppm levels for electronic-relevant carrier densities is so difficult, passivation effects are vastly more critical and dominate, to first approximation, their optoelectronic characteristics in devices.

Charge Transport Characteristics in Doped Organic Semiconductors Using Hall Effect

Numerical computations through the finite element method (FEM) are used to determine the impact of doping on carrier concentration and recombination between charges in time for organic semiconductor diodes having low mobility. The Hall effect is used to determine the effects of doping on the performance and reliability of organic semiconductor devices by accurately modeling these processes. In this work, the number density of charge carriers and Hall voltages are computed for n-type doped semiconductors with two different recombination processes, such as non-Langevin and Langevin-type. The findings reveal that in the Langevin system with β′=1, the number density of charge carriers is almost five and four times lower compared with the non-Langevin system with β′=0.01 for increasing dopant concentrations of Npd = 1 and 3, respectively. The Langevin system also had lower Hall voltages than the steady-state and non-Langevin systems for different magnetic fields with dopants, and the non-Langevin system had nearly identical Hall voltages as the steady-state case. The outcome of the current work provides insights into charge transportation mechanisms in low-mobility doped organic semiconductors with Hall effect measurements to improve device efficiency.

Ionic liquid additive induced holistic trap-passivation for enhanced charge transport in lead-halide perovskite-based transistors

Incorporating ionic liquid additives into perovskite-based electronic devices has been considerably demonstrated to improve device performance and stability via synergistic passivation effects. However, the advantages and understanding of ionic additives in perovskite field-effect transistors (FETs) have been explored far less. Herein, holistic trap-passivation is reported in a poly(3-hexylthiophene)-functionalized electrolyte-gated perovskite FETs with a solid-state ionic liquid (ss-IL) additive. The optimized ss-IL-incorporated methylammonium lead iodide (MAPbI3/ss-IL) FETs exhibited remarkable hole mobility of over 30 cm2 V−1 s−1 at an operating voltage of –1.5 V, attributed to suppressed lead/iodine vacancies and related traps and exhibiting excellent operational stability under ambient conditions with recoverable complex hysteresis behavior. These results demonstrate the promising synergistic impacts of the proposed trap engineering and provide a fundamental understanding of charge transport physics in doped perovskite semiconductors, essential for advancing their application as transistor-based devices.

Intralayer/Interlayer Codoping Stabilizes Polarity Modulation in 2D Semiconductors for Scalable Electronics.

2D semiconductors show promise as a competitive candidate for developing future integrated circuits due to their immunity to short-channel effects and high carrier mobility at atomic layer thicknesses. The inherent defects and Fermi level pinning effect lead to n-type transport characteristics in most 2D semiconductors, while unstable and unsustainable p-type doping by various strategies hinders their application in many areas, such as complementary metal-oxide-semiconductor (CMOS) devices. In this study, an intralayer/interlayer codoping strategy is introduced that stabilizes p-type doping in 2D semiconductors. By incorporating oppositely charged ions (F and Li) with the intralayer/interlayer of 2D semiconductors, remarkable p-type doping in WSe2 and MoTe2 with air stability up to 9 months is achieved. Notably, the hole mobility presents a 100-fold enhancement (0.7 to 92 cm2 V-1 s-1) with the codoping procedure. Structural and elemental characterizations, combined with theoretical calculations validate the codoping mechanism. Moreover, a CMOS inverter and more complex logic functions such as NOR and XNOR, as well as large-area device arrays are demonstrated to showcase its applications and scalability. These findings suggest that stable and straightforward intralayer/interlayer codoping strategy with charge-space synergy holds the key to unlocking the potential of 2D semiconductors in complex and scalable device applications.

Alternative Plasmonic Materials for Fluorescence Enhancement.

Noble metals such as gold and silver have been used extensively for a range of plasmonic applications, including enhancing the fluorescence rate of a dye molecule, as evidenced by numerous experiments over the past two decades. Recently, a variety of doped semiconductors have been proposed as alternative plasmonic materials, exhibiting plasmonic resonances from ultraviolet to far-infrared. In this work, we investigate the suitability of these alternative materials for enhancing the fluorescence of a molecule. Considering nanosized spheres, we study their response under plane wave illumination and the resulting enhancement factors when coupled to a quantum emitter. Comparisons with standard plasmonic metals reveal that semiconductor materials lead to a significantly reduced, and often strongly quenched, emission of light caused by their dominant absorption, which hinders fluorescence enhancement. However, we show that enhancement may be obtained when considering poor emitting dyes and high refractive index environments. Our findings demonstrate that these alternative materials result in weaker fluorescence enhancement compared to their plasmonic counterparts. Nonetheless, there are means to compensate for this, and a reasonable enhancement can be achieved for dyes in the infrared spectrum.

Electronic Structure Of Cobalt Phosphates Co1-xmxpo4 Doped With Iron And Nickel Atoms

In this research, the electronic states, band structures, and bond properties of the framework compounds of CoPO4, Co1-xFexPO4, and Co1–xNixPO4 were investigated by the density functional theory calculations. The potential capabilities of these systems in the photocatalytic water splitting to produce hydrogen were analyzed. The spin-up electron densities of states for the CoPO4, Co1–xFexPO4, and Co1–xNixPO4 systems have band gaps of 2.7, 3.4, and 3.45 eV, respectively. The band of spin-down electron states has several energy gaps above the Fermi level. The density of states of electron with spin up near the Fermi level is obviously greater than that of electrons with spin down. In this case, localized states of electrons appear in the band gap of doped semiconductors due to impurity atoms. The calculated value of the energy at the lower edge of the conduction band for CoPO4 was –0.7 eV, which is more negative than the energy required for water splitting. Meanwhile, the calculated value of the energy at the upper edge of the valence band was 2.01 eV, which is more positive than the oxygen evolution energy of 1.23 eV.

Recent modification, mechanisms, and performance of zinc oxide-based photocatalysts for sustainable dye degradation

The textile industry, which has crucial social and economic roles, faces sustainability challenges due to the generation of abundant wastewater contaminated by dyes. A wide range of photocatalysts has been developed to degrade dyes to reduce chemical and energy consumption in the treatment of dye-contaminated wastewater. This review mainly focuses on the photocatalytic mechanism and past studies of low-cost zinc oxide (ZnO) photocatalysts with various dopants to degrade dye degradation performance. Unlike previous reviews, this review delves deeply into property changes and possible mechanisms of ZnO-based photocatalysts induced by various dopants. ZnO-based photocatalysts are commonly doped with other semiconductors, metals, and non-metallic dopants. Semiconductor dopants such as titanium dioxide (TiO2), graphitic carbon nitride (g-C3N4), and iron oxide (Fe2O3) significantly modify the band gap and broaden the spectral response range of ZnO photocatalysts. Metallic dopants, including silver (Ag), copper (Cu), and cobalt (Co), introduce plasmonic effects that enhance the electrical conductivity and photocatalytic activity. Conversely, non-metallic dopants, especially carbon nanomaterials and sulfur (S), enable the adjustment of the band gap and surface properties of ZnO. Photocatalytic coating and thin films should be developed for photocatalyst reuse in future works.

2D g-C3N5 p-Doping of Donor Material for High-Efficiency Organic Solar Cells.

Molecular doping of organic semiconductor is a great strategy for significantly regulating the electronic band structure of organic semiconductor while increasing charge mobility and carrier concentration. Here, a facile strategy is presented by introducing 2D g-C3N5 as a p-dopant into PM6, improving the charge mobility and hole carrier concentration of PM6. Moreover, the electron transfer between PM6 and g-C3N5 can effectively downshift the Fermi energy level and highest occupied molecular orbital (HOMO) energy level of PM6, which leads to the increase the built-in electric field of organic solar cells (OSCs). The addition of g-C3N5 also effectively enhances the crystallization of active layer, thereby improving the stability of OSCs. As a result, a champion bulk-heterojunction (BHJ) and layer-by-layer (LbL) structure OSCs are successfully achieved featuring a high-power conversion efficiency of 18.10%/18.25%, simultaneously having excellent device stability. This work shows that introducing a low concentration dopant into organic donor is an effective method for improving the electrical performance of organic donor and the efficiency of OSCs.

High Efficiency n-Type Doping of Organic Semiconductors by Cation Exchange.

Achieving efficient doping in n-type conjugated polymers is crucial for their application in electronic devices. In this study, an n-type doping method is developed based on cation exchange that maintains a high doping level while ensuring a high degree of structural order, leading to significantly improved electrical conductivity. By investigating various dopants and ionic liquids, it is discovered that the choice of dopant influences doping efficiency, while the selection of ionic liquid affects cation exchange efficiency. Through careful selection of suitable dopants and ionic liquids, High doping levels are achieved remarkably in a short period, resulting in the highest conductivity (nearly 1×10- 2Scm-¹) compared to other doping methods for poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (N2200). The findings highlight the robustness and efficiency of cation exchange doping as an effective approach for achieving high-quality n-type doping in conjugated polymers, thereby opening new avenues for the development of advanced polymer-based electronic devices.

The critical role of energetic fluctuations in charge separation for efficient molecular doping of organic semiconductors

The critical role of energetic fluctuations in charge separation for efficient molecular doping of organic semiconductors

Solving the Asymmetric Doping for Wide-Gap Semiconductors by Host Functionalization: Quantum Engineering Strategy.

Asymmetric doping of wide-gap semiconductors has long been a major challenge, hindering their wider applications. Despite numerous attempts to address this issue through engineering doping levels, the results were still inconclusive. In this work, we propose a quantum engineering strategy based on the state-of-the-art spin-polarized HSE06 hybrid functional method. The local band offset between the host and quantum structures can considerably compensate for the large carrier activation energy (Ea). We chose the system of the AlN host embedded by GaN quantum dots as an example to validate the feasibility of this strategy. The Ea of Si (n-type) and Be (p-type) dopants can be reduced from 222 and 404 meV to negative values and 2 meV, respectively. Therefore, electron and hole density can be increased to more than 1019 and 1020 cm-3, respectively. We also tested potential dopants (C and Ge for the n-type, Mg and Ca for the p-type), and the technique is equally effective. This mechanism can also be used to understand the experimental observations of the superlattice doping strategy. Overall, our study demonstrates that the quantum engineering strategy provides a potential solution to overcome the asymmetric doping problem for universal wide-gap semiconductors and supports a feasible pathway for more efficient devices in the future.

On the Bulk Photovoltaic Effect in the Characterization of Strained Germanium Microstructures

Strain engineering serves as an effective method for optimizing electronic and optical properties in semiconductor devices, with applications including the enhancement of optical emission in Ge and GeSn‐based devices, improvement of carrier mobility, and second harmonic generation in silicon photonics structures. Current methods for deformation characterization in semiconductors, such as X‐ray diffraction and Raman spectroscopy, often require bulky and expensive setups and are limited in vertical resolution. Consequently, techniques capable of measuring lattice strain while overcoming these drawbacks are highly desirable. This study proposes a proof of concept for a cost‐effective, compact, fast, and non‐destructive approach to probe non‐uniform strain fields and additional material properties by exploiting the bulk photovoltage effect. The method is benchmarked with an array of silicon nitride stripes deposited under varying pressure conditions on a germanium substrate. Initially, their surface strains are verified through Raman spectroscopy. The deformations are replicated in a finite element method platform by integrating mechanical simulations with deformation potential theory, thereby estimating the band edge energy landscape. Finally, the study discusses the theoretical behavior of the photovoltage signal, considering semiconductor properties, defects, doping, and deformation. The findings offer insights into the development of advanced techniques for strain and transport analysis in semiconductor materials.

ScAlInN/GaN heterostructures grown by molecular beam epitaxy

Rare-earth (RE) elements doped III-nitride semiconductors have garnered attention for their potential in advanced high-frequency and high-power electronic applications. We report on the molecular beam epitaxy of quaternary alloy ScAlInN, which is an encouraging strategy to improve the heterointerface quality when grown at relatively low temperatures. Monocrystalline wurtzite phase and uniform domain structures are achieved in ScAlInN/GaN heterostructures, featuring atomically sharp interface. ScAlInN (the Sc content in the ScAlN fraction is 14%) films with lower In contents (less than 6%) are nearly lattice matched to GaN, exhibiting negligible in-plane strain, which are excellent barrier layer candidates for GaN high electron mobility transistors (HEMTs). Using a 15-nm-thick Sc0.13Al0.83In0.04N as a barrier layer in GaN HEMT, a two-dimensional electron gas density of 4.00 × 1013 cm−2 and a Hall mobility of 928 cm2/V s, with a corresponding sheet resistance of 169 Ω/□, have been achieved. This work underscores the potential of alloy engineering to adjust lattice parameters, bandgap, polarization, interfaces, and strain in emerging RE-III-nitrides, paving the way for their use in next-generation optoelectronic, electronic, acoustic, and ferroelectric applications.

High temperature ferrimagnetic semiconductors by spin-dependent doping in high temperature antiferromagnets

To realize room temperature ferromagnetic (FM) semiconductors is still a challenge in spintronics. Many antiferromagnetic (AFM) insulators and semiconductors with high Neel temperature TN are obtained in experiments, such as LaFeO3, BiFeO3, etc. High concentrations of magnetic impurities can be doped into these AFM materials, but AFM state with very tiny net magnetic moments was obtained in experiments because the magnetic impurities were equally doped into the spin up and down sublattices of the AFM materials. Here, we propose that the effective magnetic field provided by a FM substrate could guarantee the spin-dependent doping in AFM materials, where the doped magnetic impurities prefer one sublattice of spins, and the ferrimagnetic (FIM) materials are obtained. To demonstrate this proposal, we study the Mn-doped AFM insulator LaFeO3 with FM substrate of Fe metal by the density functional theory (DFT) calculations. It is shown that the doped magnetic Mn impurities prefer to occupy one sublattice of the AFM insulator and introduce large magnetic moments in La(Fe, Mn)O3. For the AFM insulator LaFeO3 with high TN = 740 K, several FIM semiconductors with high Curie temperature TC > 300 K and the band gap less than 2 eV are obtained by DFT calculations when 1/8 or 1/4 Fe atoms in LaFeO3 are replaced by the other 3d, 4d transition metal elements. The large magneto-optical Kerr effect (MOKE) is obtained in these LaFeO3-based FIM semiconductors. In addition, the FIM semiconductors with high TC are also obtained by spin-dependent doping in some other AFM materials with high TN, including BiFeO3, SrTcO3, CaTcO3, etc. Our theoretical results propose a way to obtain high TC FIM semiconductors by spin-dependent doping in high TN AFM insulators and semiconductors.

Controllable p- and n-type behaviours in emissive perovskite semiconductors.

Reliable control of the conductivity and its polarity in semiconductors is at the heart of modern electronics1-7,and has led to key inventions including diodes, transistors, solar cells, photodetectors, light-emitting diodes and semiconductor lasers. For archetypal semiconductors such as Si and GaN, positive (p)- and negative (n)-type conductivities are achieved through the doping of electron-accepting and electron-donating elements into the crystal lattices, respectively1-6. For halide perovskites, which are an emerging class of semiconductors, mechanisms for reliably controlling charge conduction behaviours while maintaining high optoelectronic qualities are yet to be discovered. Here we report that the p- and n-type characteristics in a wide-bandgap perovskite semiconductor can be adjusted by incorporating a phosphonic acid molecular dopant with strong electron-withdrawing abilities. The resultant carrier concentrations were more than 1013 cm-3 for the p- and n-type samples, with Hall coefficients ranging from -0.5 m3 C-1 (n-type) to 0.6 m3 C-1 (p-type). A shift of the Fermi level across the bandgapwas observed. Importantly, the transition from n- to p-type conductivity was achieved while retaining high photoluminescence quantum yields of 70-85%. The controllable doping in the emissive perovskite semiconductor enabled the demonstration of ultrahigh brightness (more than 1.1 × 106 cd m-2) and exceptional external quantum efficiency (28.4%) in perovskite light-emitting diodes with a simple architecture.

(Invited) Plasmon Induced Hot Electron Transfer from Doped Semiconductor Nanocrystals

In recent years, a new class of plasmonic materials based on doped semiconductor NCs has been developed. Similar to noble metals, localized surface plasmon resonances in doped semiconductor NCs arises from the coherent collective oscillation of free carriers within the NCs. The wide tunability of free carrier concentration results in tunable plasmon bands spanning from the visible to mid-infrared regime and these plasmonic semiconductor NCs have been reported to drive plasmonic hot carrier photocatalysis under near IR light illumination. These reports suggest that plasmonic semiconductors is an interesting material platform for efficient near IR driven hot carrier photocatalysis. So far the reported efficiencies are low and the mechanisms of hot carrier generation, transfer and recombination are unclear. There are interesting similarities and differences between metal and semiconductor plasmonics. First, plasmons in semiconductors can decay by inter- (band gap) and intra- band plasmon decay. Furthermore, charge transfer transition in semiconductor heterostructures have been extensively reported; can plasmon decay in plasmonic-semiconductor/semiconductor junctions proceed by exciting interfacial ET across the junction, similar to the PICTT pathway reported for metal/semiconductor junctions? Second, in plasmonic semiconductor materials, where there is a lack of states within the p-semiconductor bandgap, the transferred electrons in the accepting semiconductor CB can recombine only with the VB holes in the plasmonic semiconductor. This process requires dissipation of ~ >1 eV energy, which may slow down the recombination rate. In this talk, I will discuss our recent progresses in studying plasmon induced hot electron transfer and recombination in plasmonic semiconductor/semiconductor interfaces.