Majority Carrier Type Research Articles

Influence of Solution Deposition Process on Modulating Majority Charge Carrier Type and Quality of Perovskite Thin Films for Solar Cells.

In the past ten years, extensive research has witnessed the rapid development of perovskite solar cells (PSCs) and diversified preparation processing craft. At present, the most widely used methods of preparing perovskite solar cells are the one-step method and the two-step method. The main work of this paper is to study the effect of the solution deposition process on the quality of perovskite thin films, as well as modulating majority charge carrier types. Perovskite film was prepared in air by designing different processes, which were then adequately analyzed with corresponding methods. It was demonstrated that the preparation process plays a crucial role in modulating the type of majority carrier and in achieving high-quality perovskite thin film. The one-step prepared perovskite layer is enriched in MA+, leading to a P type majority carrier type thin film. The two-step prepared perovskite layer is enriched in Pb2+, leading to a N type majority carrier type thin film. In addition, we found that the one-step method caused PbI2 residue due to component segregation, which seriously affects the interface and film quality of the perovskite layer. This work aims to modulate the majority carrier type of perovskite film through different preparation processes, which can lay the foundation for the study of homojunction perovskite solar cells to improve the device performance of PSCs.

Magnetoresistance, magnetoimpedance, magnetothermopower, and photoconductivity in silver-doped manganese sulfides

New multifunction materials in the AgXMn1‒XS (Х = 0.05) system have been synthesized and investigated in the temperature range of 77‒500 K in magnetic fields up to 12 kOe. Near the temperature of the magnetic transition (ТN = 176 K), the anomalous behavior of the temperature dependence of magnetization has been observed and has been attributed to the formation of ferrons. An analysis of the infrared spectroscopy data and I‒V characteristics has revealed the spin-polaron subband splitting. Several conductivity channels have been found from the impedance spectra. The temperature and magnetic field dependences of the carrier relaxation time have been obtained. The magnetoresistance (−21%), magnetoimpedance (−65%), magnetothermopower (−40%), and photoconductivity effects have been detected. The majority carrier type, density, and mobility have been determined from the Hall-effect measurement data. The observed effects have been explained using a ferron model.

Majority carrier type inversion in the FeSe family and a ‘doped semimetal’ scheme in iron-based superconductors

The field and temperature dependencies of the longitudinal and Hall components of resistivity have been studied for high-quality FeSe1–xSx (x up to 0.14) single crystals. A quasiclassical analysis of the experimental data indicates a strong variation of electron and hole concentrations under the studied isovalent substitution and a clear trend towards the majority carrier type inversion. On this basis, we propose a ‘doped semimetal’ scheme for the superconducting phase diagram of the FeSe family, which can probably be applied to other iron-based superconductors. In this scheme, the two local maxima of the superconducting temperature can be associated with the Van Hove singularities of a simplified semi-metallic electronic structure. A multicarrier analysis of the experimental data also reveals the presence of a tiny and highly mobile electron band for all the samples studied. Substitution for sulfur in the studied range leads to one order decreasing in the density of highly mobile electrons, from 3% to 0.2% of the total carrier concentration. The mobility of these carriers does not depend on impurities, which may indicate an enhanced electron–phonon interaction and allows us to consider the highly mobile carriers as a possible source of unusual acoustic properties of FeSe.

Ligand-Mediated Band Engineering in Bottom-Up Assembled SnTe Nanocomposites for Thermoelectric Energy Conversion.

The bottom-up assembly of colloidal nanocrystals is a versatile methodology to produce composite nanomaterials with precisely tuned electronic properties. Beyond the synthetic control over crystal domain size, shape, crystal phase, and composition, solution-processed nanocrystals allow exquisite surface engineering. This provides additional means to modulate the nanomaterial characteristics and particularly its electronic transport properties. For instance, inorganic surface ligands can be used to tune the type and concentration of majority carriers or to modify the electronic band structure. Herein, we report the thermoelectric properties of SnTe nanocomposites obtained from the consolidation of surface-engineered SnTe nanocrystals into macroscopic pellets. A CdSe-based ligand is selected to (i) converge the light and heavy bands through partial Cd alloying and (ii) generate CdSe nanoinclusions as a secondary phase within the SnTe matrix, thereby reducing the thermal conductivity. These SnTe-CdSe nanocomposites possess thermoelectric figures of merit of up to 1.3 at 850 K, which is, to the best of our knowledge, the highest thermoelectric figure of merit reported for solution-processed SnTe.

The Fermi surface geometrical origin of axis-dependent conduction polarity in layered materials.

Electronic materials generally exhibit a single isotropic majority carrier type, electrons or holes. Some superlattice1,2 and hexagonal3-5 materials exhibit opposite conduction polarities along in-plane and cross-plane directions due to multiple electron and hole bands. Here, we uncover a material genus with this behaviour that originates from the Fermi surface geometry of a single band. NaSn2As2, a layered metal, has such a Fermi surface. It displays in-plane electron and cross-plane hole conduction in thermopower and exactly the opposite polarity in the Hall effect. The small Nernst coefficient and magnetoresistance preclude multi-band transport. We label this direction-dependent carrier polarity in single-band systems 'goniopolarity'. We expect to find goniopolarity and the Fermi surface geometry that produces it in many metals and semiconductors whose electronic structure is at the boundary between two and three dimensions. Goniopolarity may enable future explorations of complex transport phenomena that lead to unprecedented device concepts.

Two-dimensional charge carrier distribution in MoS2 monolayer and multilayers

Control of majority carrier type and concentration in transition metal dichalcogenides (TMDs) is an important goal for engineering and improving TMD-based devices. Monolayer and few-layer molybdenum disulphide (MoS2) is an n-type semiconductor due to the presence of electron-donating native defects whose distribution is strongly dependent on the processing history and ambient environment. However, the spatial heterogeneity of the charge carrier concentration has not yet been studied in MoS2 when implemented in devices such as field-effect transistors (FETs). Here, we present a method to extract the spatial distribution of charge carriers using Kelvin probe force microscopy of MoS2 FETs in operando. The carrier concentration in monolayer MoS2 exfoliated on SiO2/Si ranges from 1.2×1012 cm−2 to 2.3×1012 cm−2, corresponding to a three-dimensional concentration of 1018 cm−3 to 2.5×1018 cm−3. A comparable carrier concentration is obtained for few-layer MoS2, while for thicker MoS2 (>50 nm) it is an order of magnitude lower (2×1017 cm−3–4×1017 cm−3). This finding is consistent with an increased concentration of electron-donating sulfur vacancies at surfaces compared to the bulk. Thus, the reported method for measuring the carrier concentration may advance strategies for doping and improve understanding of devices and defects in 2D materials.

Conformational Domain Wall Switch

AbstractDomain walls in ferroelectric materials have tantalizing potential in disruptive memory and reconfigurable nanoelectronics technologies. Here, a ferroelectric domain wall switch with three distinct addressable resistance states is demonstrated. The device operation hinges on fully controllable and reversible conformational changes of the domain wall. As validated by atomistic simulations consistent with the experiments, using electric field, the shape—and hence the charge state—of the domain wall and ultimately its conduction are altered. Sequential nanoscale transitions of the walls are visualized directly using stroboscopic‐piezoresponse force microscopy and Kelvin probe microscopy. Anisotropic head‐to‐head domain wall injection, stabilized by the majority carrier type of the ferroelectric, BiFeO3, is identified as the key factor that enables conformational control.

A photoelectron study of annealing induced changes to workfunction and majority carrier type in pulsed laser deposited few layer WS2 films

Annealing few layer pulsed laser deposited WS2 films in sulfur increased the S/W ratio from 1.3 to 2.2, improved the mobility from 0.5 to 28 cm2 V−1 s−1, and switched the conductivity from n to p-type. The annealing induced n to p-type switch was confirmed by ultraviolet photoelectron spectroscopy which revealed a workfunction increase from 3.36 to 4.52 eV, a corresponding change in the Fermi level separation from the valence band edge, and a shift of the tungsten X-ray photoelectron spectrum to lower binding energy by ~ 1 eV. Current-voltage measurements indicated that charge injection from ohmic contacts was independent of the interfacial energy barrier, and was governed instead by tunneling from gap states associated with intrinsic point defects and surface contamination. The increased mobility with annealing is ascribed to improved stoichiometry and reduced incoherent scattering from point defects. The p-type conductivity is possibly due to excess sulfur in the form of interstitial ions.

Contact and Noncontact Measurement of Electronic Transport in Individual 2D SnS Colloidal Semiconductor Nanocrystals.

Colloidal-based solution syntheses offer a scalable and cost-efficient means of producing 2D nanomaterials in high yield. While much progress has been made toward the controlled and tailorable synthesis of semiconductor nanocrystals in solution, it remains a substantial challenge to fully characterize the products' inherent electronic transport properties. This is often due to their irregular morphology or small dimensions, which demand the formation of colloidal assemblies or films as a prerequisite to performing electrical measurements. Here, we report the synthesis of nearly monodisperse 2D colloidal nanocrystals of semiconductor SnS and a thorough investigation of the intrinsic electronic transport properties of single crystals. We utilize a combination of multipoint contact probe measurements and ultrafast terahertz spectroscopy to determine the carrier concentration, carrier mobility, conductivity/resistivity, and majority carrier type of individual colloidal semiconductor nanocrystals. Employing this metrological approach, we compare the electronic properties extracted for distinct morphologies of 2D SnS and relate them to literature values. Our results indicate that the electronic transport of colloidal semiconductors may be tuned through prudent selection of the synthetic conditions. We find that these properties compare favorably to SnS grown using vapor deposition techniques, illustrating that colloidal solution synthesis is a promising route to scalable production of nanoscale 2D materials.

Defect States Control Effective Band Gap and Photochemistry of Graphene Quantum Dots.

Graphene quantum dots (GQDs) have emerged as a new group of quantum-confined semiconductors in recent years, with possible applications as light absorbers, luminescent labels, electrocatalysts, and photoelectrodes for photoelectrochemical water splitting. However, their semiconductor characteristics, such as the effective band gap, majority carrier type, and photochemistry, are obscured by defects in this material. Herein, we use surface photovoltage spectroscopy (SPS) in combination with photoelectrochemical measurements to determine the parameters that are essential to the use of GQDs as next-generation semiconductor devices and photocatalysts. Our results show that ordered GQDs (1-6 nm) behave as p-type semiconductors, based on the positive photovoltage in the SPS measurements on Al, Au, and fluorine-doped tin oxide substrates, and generate mobile charge carriers under excitation of defect states at 1.80 eV and under band gap excitation at 2.62 eV. Chemical reduction with hydrazine removes some defects and increases the effective band gap to 2.92 eV. SPS measurements in the presence of sacrificial electron donor and acceptors show that photochemical charge carriers can be extracted and promote redox reactions. A reduced GQDs photocathode supports an unprecedented photocurrent of 50 μA cm-2 using K3Fe(CN)6 as sacrificial electron acceptor. Additionally, while pristine GQDs do not photoreduce protons under visible light, hydrazine-treated GQDs generate H2 from aqueous methanol under visible and UV light (0.04% quantum efficiency at 375 nm) without added co-catalysts. These findings are relevant to the use of GQDs in photochemical and photovoltaic energy-conversion systems.

Liquid phase exfoliated graphene for electronic applications

Graphene dispersions were prepared using the liquid phase exfoliation method with three different surfactants. One surfactant was used from each of the surfactant types, anionic, cationic, and non-ionic; those used, were sodium dodecylbenzene sulfonate (SDBS), cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP), respectively. Raman spectroscopy was used to investigate the number of layers and the nature of any defects present in the exfoliated graphene. The yield of graphene was found to be less with the non-ionic surfactant, PVP. The deconvolution of 2D peaks at ~2700 cm−1 indicated that graphene prepared using these surfactants resulted in sheets consisting of few-layer graphene. The ratio of intensity of the D and G bands in the Raman spectra showed that edge defect density is high for samples prepared with SDBS compared to the other two, and is attributed to the smaller size of the graphene sheets, as shown in the electron micrographs. In the case of the dispersion in PVP, it is found that the sizes of the graphene sheets are highly sensitive to the concentration of the surfactant used. Here, we have made an attempt to investigate the local density of states in the graphene sheets by measuring the tunnelling current–voltage characteristics. Graphene layers have shown consistent p-type behaviour when exfoliated with SDBS and n-type behaviour when exfoliated with CTAB, with a larger band gap for graphene exfoliated using CTAB. Hence, in addition to the known advantages of liquid phase exfoliation, we found that by selecting suitable surfactants, to a certain extent it is possible to tune the band gap and determine the type of majority carriers.

High‐Quality GaSb and GaInSb Crystals Prepared by Vertical Bridgman Method

AbstractHigh‐quality GaSb and Ga1‐xInxSb (x = 0.14) crystals were grown via the vertical Bridgman (VB) method. The lattice structure, morphology, optical, and transport properties of the GaSb and GaInSb crystals were characterized. The influence of the indium doping on the physical properties of the GaSb crystal was also investigated. The results demonstrate that the indium doping maintains the zinc‐blende lattice structure of the GaSb crystal. The segregation of indium is very low, with the radial and axial concentration variation of 2.32% and 4.84%, respectively. The indium doping significantly reduces the dislocation density down to 1.275 × 103 cm−2. The band gap of the indium‐doped GaSb is reduced to 0.549 eV, consistent with the decreased infrared transmission measured by FTIR. Surprisingly, the indium doping changes the majority carrier type of the crystal, from p‐type in the pristine GaSb crystal to n‐type in the GaInSb crystal. Compared to the GaSb crystal, the GaInSb crystal shows enhanced transport properties, with carrier mobility increased to 2.512 × 103 cm2/(V•s) and resistivity reduced to 0.521 × 10−3 ohm•cm.

Energy location of Ce3+ 4f level and majority carrier type in Gd3Al2Ga3O12:Ce crystals studied by surface photovoltage spectroscopy

Gd3Al2Ga3O12:Ce (GAGG:Ce) was studied by surface photovoltage spectroscopy using the ultraviolet photoelectron spectroscopy technique with synchrotron radiation and a laser source. The lowest Ce3+ 4f level is located below the conduction band minimum by 3.02 eV. This result is supported by the excitation spectrum for photo-stimulated luminescence and is compatible with the value predicted by the vacuum-referred binding energy scheme for GAGG:Ce. It is also found that GAGG:Ce is of the p-type. The information on the energy location of the Ce3+ 4f level and majority carrier type provides us with hints on how to improve the optical properties of GAGG:Ce for photonic device applications.

Charge Dynamics and Optolectronic Properties in HgTe Colloidal Quantum Wells.

We investigate the electronic and transport properties of HgTe 2D colloidal quantum wells. We demonstrate that the material can be made p- or n-type depending on the capping ligands. In addition to the control of majority carrier type, the surface chemistry also strongly affects the photoconductivity of the material. These transport measurements are correlated with the electronic structure determined by high resolution X-ray photoemission. We attribute the change of majority carriers to the strong hybridization of an n-doped HgS layer resulting from capping the HgTe nanoplatelets by S2- ions. We further investigate the gate and temperature dependence of the photoresponse and its dynamics. We show that the photocurrent rise and fall times can be tuned from 100 μs to 1 ms using the gate bias. Finally, we use time-resolved photoemission spectroscopy as a probe of the transport relaxation to determine if the observed dynamics are limited by a fundamental process such as trapping. These pump probe surface photovoltage measurements show an even faster relaxation in the 100-500 ns range, which suggests that the current performances are rather limited by geometrical factors.

Magnetotransport Properties of MnGeAs<sub>2</sub> Films

MnGeAs2 thin films were successfully deposited on GaAs(100) substrate. The films exhibited room-temperature ferromagnetism with TC ~ 330 K, based on both magnetization and resistance measurements at temperatures from 5 to 370 K. The coercive fields at 5 and 300 K were 2100 and 50 Oe. The anomalous Hall effect was observed, suggesting the existence of spin polarized carriers in MnGeAs2 thin films. The magnetoresistance (MR) measurements showed very small change (~ 0.1% at 5 K) in resistance at low temperature. The MR value at 5 K was smaller than that (~ 9% at 305 K) at room temperature (305 K). Type of majority carriers in the films was determined to be n-type by Hall measurement above the transition temperature. The effective carrier density was 1.8´1020 cm-3. The diode current-voltage characteristics were shown in a hetero-junction MnGeAs2 film on a conducting p-type GaAs substrate.

Ambipolar Barristors for Reconfigurable Logic Circuits.

Vertical heterostructures based on graphene have emerged as a unique architecture for novel electronic devices with unusual characteristics. Here we report a new design of vertical ambipolar barristors based on metal-graphene-silicon-graphene sandwich structure, using the bottom graphene as a gate-tunable "active contact", the top graphene as an adaptable Ohmic contact, and the low doping thin silicon layer as the switchable channel. Importantly, with finite density of states and weak screening effect of graphene, we demonstrate, for the first time, that both the carrier concentration and majority carrier type in the sandwiched silicon can be readily modulated by gate potential penetrating through graphene. It can thus enable a new type of ambipolar barristors with an ON-OFF ratio exceeding 103. Significantly, these ambipolar barristors can be flexibly configured into either p-type or n-type transistors and used to create integrated circuits with reconfigurable logic functions. This unconventional device structure and ambipolar reconfigurable characteristics can open up exciting opportunities in future electronics based on graphene or two-dimensional van der Waals heterostructures.

Exploring different doping mechanisms in thermoelectric polymer/carbon nanotube composites

This work compares various methods to prepare polymer/carbon nanotube (CNT) composites for thermoelectric applications, focusing on the different doping mechanisms. We first look at the general trends observed in the Seebeck coefficient and power factor for a large number of composites as a function of electrical conductivity. Then we discuss two methods of nitrogen doping the carbon nanotubes in these composites, namely either during synthesis, or afterwards by ammonolysis. Finally, we discuss doping of the carbon nanotubes through charge transfer from the polymer counterpart, including photo-induced switching of the majority carrier type. As a general remark, we note that processability is negatively influenced by some doping procedures. Best results were achieved for unfunctionalized single-walled carbon nanotubes with a high content of semiconducting CNT species.

Type-inversion as a working mechanism of high voltage MAPbBr3(Cl)-based halide perovskite solar cells.

Using several metals with different work functions as solar cell back contact we identify majority carrier type inversion in methylammonium lead bromide (MAPbBr3, without intentional doping) as the basis for the formation of a p-n junction. MAPbBr3 films deposited on TiO2 are slightly n-type, whereas in a full device they are strongly p-type. The charge transfer between the metal electrode and the halide perovskite (HaP) film is shown to determine the dominant charge carrier type of the HaP and, thus, also of the final cells. Usage of Pt, Au and Pb as metal electrodes shows the effects of metal work function on minority carrier diffusion length and majority carrier concentration in the HaP, as well as on built-in voltage, band bending, and open circuit voltage (VOC) within a solar cell. VOC > 1.5 V is demonstrated. The higher the metal WF, the higher the carrier concentration induced in the HaP, as indicated by a narrower space charge region and a smaller minority carrier diffusion length. From the analysis of bias-dependent electron beam-induced currents, the HaP carrier concentrations are estimated to be ∼ 1 × 1017 cm-3 with Au and 2-3 × 1018 cm-3 with Pt. A model in which type-inversion stretches across the entire film width implies formation of the p-n junction away from the interface, near the back-contact metal electrode. This work highlights the importance of the contact metal on device performance in that contact engineering can also serve to control the carrier concentration in HaP.

Limits of Carrier Diffusion in n-Type and p-Type CH3NH3PbI3 Perovskite Single Crystals.

Using a combination of scanning photocurrent microscopy (SPCM) and time-resolved microwave conductivity (TRMC) measurements, we monitor the diffusion and recombination of photoexcited charges in CH3NH3PbI3 perovskite single crystals. The majority carrier type was controlled by growing crystals in the presence or absence of air, allowing the diffusion lengths of electrons (LDe–) and holes (LDh+) to be directly imaged with SPCM (LDe– = 10–28 μm, LDh+ = 27–65 μm). TRMC measurements reveal a photogenerated carrier mobility (μh + μe) of 115 ± 15 cm2 V–1 s–1 and recombination that depends on the excitation intensity. From the intensity dependence of the recombination kinetics and by accounting for carrier diffusion away from the point of photogeneration, we extract a second-order recombination rate constant (krad = 5 ± 3 × 10–10 cm3/s) that is consistent with the predicted radiative rate. First-order recombination at low photoexcited carrier density (knrp-type = 1.0 ± 0.3 × 105 s–1, knrn-type = 1.5 ± 0.3 × 105 ...

Majority Carrier Type Control of Cobalt Iron Sulfide (CoxFe1–xS2) Pyrite Nanocrystals

We report the colloidal synthesis, characterization, and electronic property control of compositionally varied CoxFe1–xS2 cubic pyrite nanocrystals (NCs) and thin films formed from solution. Using drop-cast NC thin films, we demonstrate the relationship between the material composition and the majority carrier type of the nanocrystalline thin films. Measurements of the majority carrier type as a function of NC composition indicate that CoxFe1–xS2 NC thin films change from p-type to n-type between x = 0.16 and x = 0.21. Additional characterization to confirm the crystallinity, composition, size, and shape was performed using powder X-ray diffraction, Raman spectroscopy, energy dispersive X-ray spectroscopy, and scanning electron microscopy. The observed n-type behavior which accompanies the substitution of Co for Fe in these cubic pyrite nanostructures agrees with previous reports of n-type behavior occurring at even very low concentration Co doping of iron pyrite. The ability to prepare n- or p-type pyrit...