Saturation capacitance of thin oxide MOS structures and the effective surface density of states of silicon

The capacitance vs voltage curve of thin oxide (30–40 Å) MOS structures in strong accumulation was studied. The results were interpreted in terms of equivalent surface density of state masses, which was found to be 0·2 m₀ for the silicon valence band and 0·06 m₀ for the conduction band, for both 111 and 100 surfaces. The experimental density of state masses were shown to be much lower than the bulk values. Equivalent density of states masses were calculated from a surface quantization model and in this case agreement with the experiments was obtained for the valence band only.     

Accurate surface potential determination in Schottky diodes by use of correlated current and capacitance voltage measurements. Application to n–InP

Based on current voltage (I-V_g) and capacitance voltage (C-V_g) measurements, a reliable procedure is proposed to determine the effective surface potential V_d.V_g/ in Schottky diodes. In the framework of thermionic emission, our analysis includes both the effect of the series resistance and the ideality factor, even voltage dependent. This technique is applied to n-type indium phosphide (n-InP) Schottky diodes with and without an interfacial layer and allows us to provide an interpretation of the observed peak on the C-V_g measurements. The study clearly shows that the depletion width and the flat band barrier height deduced from C-V_g, which are important parameters directly related to the surface potential in the semiconductor, should be estimated within our approach to obtain more reliable information.     

Impact of Blend Morphology on Interface State Recombination in Bulk Heterojunction Organic Solar Cells

This work is a reinvestigation of the impact of blend morphology and thermal annealing on the electrical performance of regioregular‐P3HT:PC₆₀BM bulk heterojunction organic solar cells. The morphological, structural, and electrical properties of the blend are experimentally investigated with atomic force microscopy, X‐ray diffraction, and time‐of‐flight measurements. Current–voltage characteristics of photodiode devices are measured in the dark and under illumination. Finally, the existence of exponential electronic band tails due to gap states is experimentally confirmed by measuring the device spectral response in the subband gap regime. This method reveals the existence of a large density of gap states, which is partially and systematically reduced by thermal annealing. When the band tails are properly accounted for in the drift and diffusion simulations, experimentally measured charge transport characteristics, under both dark and illuminated conditions and as a function of annealing time, can be satisfactorily reproduced. This work further confirms the critical impact of tails states on the performance of solar cells.     

表面结构和生长方向对WO3纳米线电子结构影响的第一性原理研究

The effects of the surface and orientation of a WO₃ nanowire on the electronic structure are investigated by using first principles calculation based on density functional theory（DFT）.The surface of the WO3 nanowire was terminated by a bare or hydrogenated oxygen monolayer or bare WO₂ plane,and the[010]- and[001]-oriented nanowires with different sizes were introduced into the theoretical calculation to further study the dependence of electronic band structure on the wire size and orientation.The calculated results reveal that the surface structure, wire size and orientation have significant effects on the electronic band structure,bandgap,and density of states （DOS） of the WO₃ nanowire.The optimized WO₃ nanowire with different surface structures showed a markedly dissimilar band structure due to the different electronic states near the Fermi level,and the O-terminated[001] WO₃ nanowire with hydrogenation can exhibit a reasonable indirect bandgap of 2.340 eV due to the quantum confinement effect,which is 0.257 eV wider than bulk WO₃.Besides,the bandgap change is also related to the orientation-resulted surface reconstructed structure as well as wire size.     

The interface between Hg1−xCdxTe and its native oxide

The results of a study of the electrical properties of the interface between Hg_1?xCd_xTe with x = 0.21 and its native oxide at 77°K are presented. The native oxide is formed by anodic oxidation and results in an interface with reproducible properties. The surface charge, the surface mobility and the effective lifetime are obtained from galvanomagnetic measurements and are related to the semiconductor bulk parameters, the oxide thickness and the annealing conditions. The surface state charge and the metal-semiconductors work function difference are obtained from the shift of the flat band voltage of metal-oxide-semiconductor (MOS) capacitor characteristics. The interface between Hg_1?xCd_xTe and its native anodic oxide is characterized by a density of fast surface states of the order of 5 × 10¹¹cm^?2 (eV^?1) near the middle of the bandgap. The density of states increases towards the band edges to the order of 10¹³cm^?2 (eV^?1). The measured flat band voltage is approximately ?0.5 V for an oxide thickness of 500 Å and for an n-type semiconductor with an electron carrier concentration in the range 1–3 × 10¹⁵cm^?3 at 77°K. The fixed oxide surface state charge is positive for both p-type and n-type semiconductors and is of the order of 6 × 10¹¹ charges per cm^?2. The surface properties, the significance and the reproducibility of the results are evaluated.     

Empty-State Band Mapping Using Momentum-Resolved Secondary Electron Emission

Material band structures of occupied electronic states are obtainable using conventional angle-resolved photoemission experiments, leaving the unoccupied states far less explored. Here, an alternative approach is built on and expanded to investigate thermalized photoelectrons emitted from crystal surfaces. A model for electron emission is constructed and reveals the material unoccupied state band structure. Potentially applicable to any material and independent from the secondary electron generation mechanism, it is demonstrated on diamond and copper using different light sources. Moreover, the diamond indirect band gap is directly observed and the transverse effective mass at the conduction band minimum can be experimentally obtained, m_t = (0.21 ± 0.015) m_e. This offers a convenient path for angle-resolved photoemission data interpretation and empty-state information extraction.     

Towards barrier height modulation in HfO2/TiN by oxygen scavenging - Dielectric defects or metal induced gap states?

The band alignment between a dielectric and a metal gate is crucial as it controls the MOSFET threshold voltage as well as the leakage in metal-insulator-metal (MIM) structure. In the ideal Schottky-Mott model the barrier height should be controlled only by the workfunction and the electron affinity of the materials considered. However, this seems the case only for few insulating materials other than SiO₂ (i.e., Fermi level pinning).The most popular explanation invokes metal-induced gap states (MIGS), where electron states from the bulk of a metal tails into the insulator. The MIGS hypothesis explains a rather large series of experimental results and, importantly, predicts that the MI barrier height will mostly be controlled by the energy distribution of electron states in the bulk of the contacting metal and dielectric. In this paper, we analyze the band alignment of contacting metal (TiN) and dielectric (HfO₂) by using internal photoemission. It will be shown that defects in the dielectric rather than MIGS control the barrier height.     

Surface states at the nGaAsSiO2 interface from conductance and capacitance measurements

Conductance and capacitance measurements have been used to investigate the interface properties of MOS capacitors formed by depositing an insulating layer of SiO₂ on n-type GaAs. The surface potential as a function of applied bias is evaluated using results of high and low frequency capacitance measurements and the two methods are found to yield roughly similar results. The interface state density evaluated from the conductance and capacitance measurements is found to peak near the center of the band gap and also near the conduction band edge. Plots of conductance vs frequency indicate the presence of both fast and slow interface states in these materials.     

Elucidating the Origins of Subgap Tail States and Open‐Circuit Voltage in Methylammonium Lead Triiodide Perovskite Solar Cells

Recombination via subgap trap states is considered a limiting factor in the development of organometal halide perovskite solar cells. Here, the impact of active layer crystallinity on the accumulated charge and open‐circuit voltage (V_oc) in solar cells based on methylammonium lead triiodide (CH₃NH₃PbI₃, MAPI) is demonstrated. It is shown that MAPI crystallinity can be systematically tailored by modulating the stoichiometry of the precursor mix, where small quantities of excess methylammonium iodide (MAI) improve crystallinity, increasing device V_oc by ≈200 mV. Using in situ differential charging and transient photovoltage measurements, charge density and charge carrier recombination lifetime are determined under operational conditions. Increased V_oc is correlated to improved active layer crystallinity and a reduction in the density of trap states in MAPI. Photoluminescence spectroscopy shows that an increase in trap state density correlates with faster carrier trapping and more nonradiative recombination pathways. Fundamental insights into the origin of V_oc in perovskite photovoltaics are provided and it is demonstrated why highly crystalline perovskite films are paramount for high‐performance devices.     

Electronic states on silicon surface after deposition and annealing of SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films

The spectrum of the photoconductivity induced by the polarization field of charges at surface states and traps in the film bulk has been analyzed to determine the energy band diagram at the c-Si-SiO _x interface and the changes in the electronic states after the film annealing. It is found that the energy bands are bent at the Si-SiO _x interface and the Si surface is enriched in electrons. In equilibrium the photocurrent peak at 1.1 eV is due to the band-to-band transitions in the silicon part of the interface. Annealing shifts the peak to higher energies; this shift increases with an increase in the annealing temperature from 650 to 1000°C. This effect is accompanied by a decrease in the photocurrent at ≤1.1 eV and weakening of the band-edge photoluminescence near the Si surface. The changes revealed are explained by the formation of an oxide layer with Si nanoclusters at the Si-SiO _x interface upon annealing. This process is caused by oxygen diffusion from the SiO _x film, which occurs mainly via defects on the Si wafer surface. The photoconductivity spectrum of the samples charged by short-term application of a negative potential to silicon exhibits electronic transitions in the SiO _x film, both from the matrix electronic states and from the states of the defects and Si nanoclusters in the film.     

Photo-thermal probing of Si-SiO2 surface centers—II: Experiment

The results of photo-thermal probing measurements are presented and interpreted to characterize the Si-SiO₂ surface center photoresponse and to provide information relevant to the evaluation of existing surface state models. Data is first presented to indisputably confirm the facts that surface center photoemission had indeed been observed and that the photoresponse could be isolated from competing relaxation mechanisms. The subsequent presentation is devoted primarily to an examination and analysis of photovoltage vs time data characterizing the surface center response. From the analysis it is concluded that two distinct types of surface centers are quasi-continuously distributed in energy over the central portion of the Si band gap, with both types of states acting as if they were positioned right at the Si-SiO₂ interface. The feature distinguishing the two types of states, referred to as A-states and B-states, is a widely different photocapture cross section at any given band gap energy, measured photocapture cross sections being on the order of 10^?19 cm² and 10^?20 cm² for A- and B-states, respectively. B-states, which exhibit the longer photorelaxation time constant, dominate the response in the upper portion of the band gap, while A-states dominate the response below approximately E_v + 0.3 eV. Finally, the photocapture cross section of each type of state was found to increase systematically toward the band edges due to a Lucovsky-type energy dependence.     

Vertical Phase Separated Cesium Fluoride Doping Organic Electron Transport Layer: A Facile and Efficient “Bridge” Linked Heterojunction for Perovskite Solar Cells

In perovskite solar cells (PSCs), the interfaces of the halide perovskite/electron transport layer (ETL) and ETL/metal oxide electrode (MOE) always attract and trap free carriers via the surface electrostatic force, altering quasi‐Fermi level (E_Fq) splitting of contact interfaces, and significantly limit the charge extraction efficiency and intrinsic stability of devices. Herein, a graded “bridge” is first reported to link the MOE and perovskite interfaces by self vertical phase separation doping (PSD), diminishing the side effect of notorious ionic defects via both reinforced interface E_bi and the vacancies filling. Experimental and theoretical results prove that the inhomogeneous distribution of CsF in the bulk or surface of PC₆₁BM would not only form metal–oxygen (M–O) dipole on MOE, reinforcing the interface E_bi, but also create a graded energy bridge to alleviate the disadvantage of band offset raised by the enhanced interface E_bi, which significantly avoid the carrier accumulation and recombination at defective interfaces. Employing PSD, the power conversion efficiency of the devices approaches 21% with a high open‐circuit voltage (1.148 V) and delivers a high stability of 89% after aging 60 days in atmosphere without encapsulation, which is the highest efficiency of organic electron transport layers for n–i–p PSCs.     

Effects of tail states on the conduction mechanisms in silicon carbide thin films with high carbon content

Hydrogenated amorphous silicon carbide (a-SiC_x:H) films of different carbon content (x) were deposited by radio frequency plasma enhanced chemical vapor deposition (PECVD) system. Apart from the X-ray photoelectron spectroscopy (XPS) and UV-Visible transmission analyses, the resistivity measurements between 293 K and 450 K were emphasized to assess the eventual transport mechanisms. The film resistivities are unexpectedly found relatively low, especially for high carbon content. In the frame of exclusive band conduction, the apparent thermal activation energies, evaluated from Arrhenius type plot remain too low compared to half values of the optical gaps.Numerical analyses were undertaken by extending conduction from the band conduction about the mobility edge inside the band gap by including the nearest neighbor hopping (NNH) conduction across the localized tail states. By successfully fitting the formulated conductivity expression to the experimental results, parameters such as tail states distributions, true activation energies to the mobility edge have been retrieved.     

Effects of Nonradiative Losses at Charge Transfer States and Energetic Disorder on the Open‐Circuit Voltage in Nonfullerene Organic Solar Cells

The considerable improvement on the power conversion efficiency (PCE) for emerging nonfullerene polymer solar cells is still limited by considerable voltage losses that have become one of the most significant obstacles in further boosting desired photovoltaic performance. Here, a comprehensive study is reported to understand the impacts of charge transport, energetic disorder, and charge transfer states (CTS) on the losses in open‐circuit voltage (V_oc) based on three high performing bulk heterojunction solar cells with the best PCE exceeding 11%. It is found that the champion poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene)‐co‐(1,3‐di(5‐thiophene‐2‐yl)‐5,7‐bis(2‐ethylhexyl)‐benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione))] (PBDB‐T):IT‐M solar cell (PCE = 11.5%) is associated with the least disorder. The determined energetic disorder in part reconciles the difference in V_oc between the solar cells. A reduction is observed in the nonradiative losses (ΔV_nonrad) coupled with the increase of energy of CTS for the PBDB‐T:IT‐M device, which may be related to the improved balance in carrier mobilities, and partially can explain the gain in V_oc. The determined radiative limit for V_oc combined with the ΔV_nonrad generates an excellent agreement for the V_oc with the experimental values. The results suggest that minimizing the energetic disorder related to transport and CTS is critical for the mitigation of V_oc losses and improvements on the device performance.     

Improvements in the Quasi-static Capacitance–Voltage Characterization of Semiconductor–Insulator Interface States (Si/SiO2)

The quasi-static capacitance–voltage determination of the electron density of states as a function of energy at the semiconductor–insulator interface is addressed. The respective effects are analyzed of random and systematic errors in a measured capacitance–voltage characteristic on the interface-state distribution derived. The random errors show up as fluctuations that grow indefinitely in magnitude as the energy approaches either band edge. Systematic errors are manifested in under- and overshoots near the band edges. The most important are the systematic errors associated with the estimation of the insulator capacitance and the identification of the relationship between the semiconductor surface potential and the applied voltage. A method for minimizing the errors is proposed. It is noted that the method should enable one to substantially expand the accessible energy range and to significantly improve the accuracy to which the density of states is evaluated. These advantages are confirmed by an experiment on the Si/SiO₂ interface. It is found that the energy range can be made as wide as about 0.9 eV and the accuracy of the semiconductor surface potential can be improved to about 0.1 meV, so that the integrated density of states can be determined to within about 5 × 10⁷ cm^–2. It is inferred from the experimental data that the interface states are concentrated near the conduction band edge and are due to positive oxide fixed ions rather than P _bcenters. The ions should act as electron traps involved in tunnel electron exchange with the conduction band of the silicon.     

MOS capacitors obtained by wet oxidation of n-type 4H-SiC pre-implanted with nitrogen

The manufacture process and the electrical characterization of MOS devices fabricated by wet oxidation of N⁺ implanted n-type 4H-SiC are here presented. Different implantation fluence and energy values were used with the aims to study the effect of the N concentration both at the SiO₂/SiC interface and within the SiO₂ film. High doses, able to amorphise a surface SiC layer to take advantage of the faster oxidation rate of amorphous with respect to crystalline SiC, were also evaluated. The electrical quality of the SiO₂/SiC system was characterized by capacitance-voltage measurements of MOS capacitors. The analyses of the collected data show that only the implanted N which is located at the oxide-SiC interfaces is effective to reduce the interface states density. On the contrary, the interface states density remains high (the same of an un-implanted reference sample) when the implanted N is completely embedded in the region consumed by the oxidation. Furthermore, none generation of fixed positive charges in the oxide was found as a consequence of the different N concentrations enclosed in the oxide films. These results were independent of the amorphisation of the implanted layer by the N⁺ ions. Our results demonstrate that by using a suitable N ion implantation and an appropriate wet oxidation treatment, it is possible to obtain a reduced thermal budget process able to decrease the interface state density near the conduction band edge. The proposed approach should be interesting for the development of the MOSFET technology on SiC.     

GGA U方法研究应变对纤锌矿ZnO能带结构的影响

基于第一性原理密度泛函理论和GGA U方法,以Zn1-xMgxO衬底的应变为例,计算了应变ZnO体材料的能带结构。同时研究了应力对ZnO材料的禁带宽度、价带分裂能以及电子和空穴有效质量的影响。研究结果表明,Mg组分不大于0.3时,ZnO/Znl-xMgxO材料禁带宽度随应力增大而增大,该结论与实验研究结果相符合。沿[00k] 和[k00]晶向,导带电子有效质量随应力增加而稍有增大,“场致分裂带”空穴有效质量随应力增大明显减小,而“轻空穴带”和“重空穴带”空穴有效质量几乎不随应力改变而变化。     

A single-frequency approximation for interface-state density determination

Fast interface state densities in the SiSi₂ system can be determined by measurements of the MIS capacitor admittance. Traditional detailed analysis require elaborate frequency dependent techniques. The more commonly used approximation techniques are difficult to interpret for interface state densities less than 1 × 10¹¹ eV^?1 cm^?2. We present here a new single frequency technique as an approximation method which provides quantitative criteria on the quality of such interfaces. The data required are a single high frequency capacitance vs voltage measurement and a corresponding conductance vs voltage measurement. The validity of this technique is best demonstrated in a three-dimensional plot of conductance, frequency and voltage. This also gives added insight into the relationship between the temporal and thermodynamic properties of interface electronic states. Comparison of results using this approximation to more detailed treatments demonstrates the validity of this new method for low surface state density determination in a range from 7 × 10⁹ eV^?1 cm^?2 to 8 × 10¹¹ eV^?1 cm^?2.     

Record 1.0 V open‐circuit voltage in wide band gap chalcopyrite solar cells

Tandem solar cell structures require a high‐performance wide band gap absorber as top cell. A possible candidate is CuGaSe₂, with a fundamental band gap of 1.7 eV. However, a significant open‐circuit voltage deficit is often reported for wide band gap chalcopyrite solar cells like CuGaSe₂. In this paper, we show that the open‐circuit voltage can be drastically improved in wide band gap p‐Cu(In,Ga)Se₂ and p‐CuGaSe₂ devices by improving the conduction band alignment to the n‐type buffer layer. This is accomplished by using Zn_1−x Sn_x O_y , grown by atomic layer deposition, as a buffer layer. In this case, the conduction band level can be adapted to an almost perfect fit to the wide band gap Cu(In,Ga)Se₂ and CuGaSe₂ materials. With an improved buffer band alignment for CuGaSe₂ absorbers, evaporated in a 3‐stage type process, we show devices exhibiting open‐circuit voltages up to 1017 mV, and efficiencies up to 11.9%. This is to the best of our knowledge the highest reported open‐circuit voltage and efficiency for a CuGaSe₂ device. Temperature‐dependent current‐voltage measurements show that the high open‐circuit voltage is explained by reduced interface recombination, which makes it possible to separate the influence of absorber quality from interface recombination in future studies.     

Magnetic Second-Order Topological Insulator: An Experimentally Feasible 2D CrSiTe3

2D second-order topological insulators (SOTIs) have sparked significant interest, but currently, the proposed realistic 2D materials for SOTIs are limited to nonmagnetic systems. In this study, for the first time, a single layer of chalcogenide CrSiTe₃—an experimentally realized transition metal trichalcogenide is proposed with a layer structure—as a 2D ferromagnetic (FM) SOTI. Based on first-principles calculations, this study confirms that the CrSiTe₃ monolayer exhibits a nontrivial gapped bulk state in the spin-up channel and a trivial gapped bulk state in the spin-down channel. Based on the higher-order bulk–boundary correspondence, it demonstrates that the CrSiTe₃ monolayer exhibits topologically protected corner states with a quantized fractional charge ($\frac{e}{3}$) in the spin-up channel. Notably, unlike previous nonmagnetic examples, the topological corner states of the CrSiTe₃ monolayer are spin-polarized and pinned at the corners of the sample in real space. Furthermore, the CrSiTe₃ monolayer retains SOTI features when the spin–orbit coupling (SOC) is considered, as evidenced by the corner charge and corner states distribution. Finally, by applying biaxial strain and hole doping, this study transforms the magnetic insulating bulk states into spin-gapless semiconducting and half-metallic bulk states, respectively. Importantly, the topological corner states persist in the spin-up channel under these conditions.