Microscopic evidence for the modification of the electronic structure at grain boundaries of Cu(In(1-x),Ga(x))Se2 films

We investigated the electronic properties around grain boundaries of polycrystalline Cu(In(1-x),Ga(x)Se(2)) films as a function of Ga content, using scanning tunneling spectroscopy. Spectra acquired on samples with low Ga content (x=0 and 0.33) reveal downward band bending with respect to adjacent p-type grains, suggesting type inversion at the surface of grain boundaries. Such a behavior was not observed for samples with high Ga contents. These results are consistent with our atomic force microscopy data and may shed light on the origin of the x-dependent efficiency for polycrystalline Cu(In(1-x),Ga(x)Se(2))-based solar cells.     

Two different effects of Na on Cu2ZnSnS4 thin-film solar cells

Among the many factors that affect the characteristics of Cu₂ZnSnS₄ thin-film solar cells, the effects of Na were examined. Because Na passivates the grain boundaries (GBs) in absorber layers, the GBs increase the minority carrier collection by providing a current pathway through which the minority carriers can reach the buffer and window layer and be collected. However, excess Na remains in the absorber layer and diffuses into the buffer and window layers, where it acts as an impurity and traps the minority carriers, thus decreasing the solar cell characteristics. By applying an annealing process after the deposition of the buffer and window layers, the Na content could be decreased. By improving the solar cell characteristics, a power conversion efficiency of 6.43% was achieved.     

Scanning tunneling spectroscopy of charge effects on semiconductor surfaces and atomic clusters

We have used scanning tunneling microscopy and scanning tunneling spectroscopy at liquid helium temperature to study the electronic structure of in situ cleaved, (110) oriented surfaces of InAs single crystals. Both unperturbed, atomically flat areas and areas with an atomic-size defect cluster have been investigated. We show that the anomalous behavior of the local tunneling conductivity, which indicates a pronounced enhancement of the semiconductor band gap for the flat areas, is consistent with band bending induced by charges localized at the apex of the tip. Atomic-size defect clusters contain additional charges which modify the band bending; this explains the different behavior of the tunneling conductivity near the defect cluster. The experimentally observed oscillations of the tunneling conductivity near the band gap edges can be directly related to resonant tunneling through quantized surface states which appear because of the band bending. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 2, 130–135 (25 January 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Investigation of local electronic transport and surface potential distribution of Cu(In,Ga)Se2 thin-films

Local current mapping and surface potential distributions on polycrystalline Cu(In,Ga)Se₂ (CIGS) films are investigated by conductive atomic force microscopy and Kelvin probe force microscopy. The two kinds of samples fabricated by co-evaporation had extremely different conversion efficiencies of 10% and 0.2% for stoichiometric and Cu- and Se-deficient compositions, respectively. We examined the microscopic reasons for the differences in the local electrical properties. Current mapping and current–voltage behaviors were measured at intragrain regions (IGs) and grain boundaries (GBs). Electronic transport between a Pt scanning probe and the CIGS layer is explained by the Schottky conduction mechanism. The surface potential distribution shows an intriguing relation with topological variation, inferring that a local built-in potential is possibly formed on positively charged GBs. The surface potential is about 100 mV, which shows energy band bending near GBs in the films. Exciton separation near GBs is explained by the bending of the conduction and valence bands, which is sensitive to compositional and structural inhomogeneities.     

Texture and electronic activity of grain boundaries in Cu(In,Ga)Se2 thin films

The influence of different film textures on the electronic properties of polycrystalline Cu(In,Ga)Se₂ absorbers is studied by measuring the laterally resolved optoelectronic properties of differently textured Cu(In,Ga)Se₂ films with Kelvin probe force microscopy and cathodoluminescence. The grain boundaries in (112)- and (220/204)-textured films behave differently. The work-function profile measured with the Kelvin probe across a grain boundary in (112)-textured films shows a dip indicating positive charges at the grain boundaries. In panchromatic cathodoluminescence mappings in a transmission electron microscope, such grain boundaries appear dark, i.e. the strongly reduced luminescence indicates that the grain boundaries represent strong non-radiative recombination centers. In contrast, grain boundaries in (220/204)-textured films give rise to a dip or a step in the work function indicating slightly negative charge or neutrality. Cathodoluminescence is reduced at such grain boundaries, but less dramatically than in the (112)-textured case. However, when Na is present in the (220/204)-textured films, the grain boundaries are almost invisible in cathodoluminescence mappings. This strong passivating action of Na occurs only in the (220/204)-textured films, due to a particular grain-boundary population. In (112)-textured films and films without pronounced texture, this passivation effect is much less noticeable. PACS 73.50.Gr; 73.61.Ga; 78.60.Hk; 87.64.Dt     

Chemical and electronic properties of sulfur-passivated InAs surfaces

Treatment with ammonium sulfide ((NH₄)₂S_x) solutions is used to produce model passivated InAs(0 0 1) surfaces with well-defined chemical and electronic properties. The passivation effectively removes oxides and contaminants, with minimal surface etching, and creates a covalently bonded sulfur layer with good short-term stability in ambient air and a variety of aqueous solutions, as characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and Hall measurements. The sulfur passivation also preserves the surface charge accumulation layer, increasing the associated downward band bending.     

Electron backscatter diffraction study of changes in the grain structure of Ni3Fe ordering alloy upon an A1 → L12 phase transition

The rearrangement of the grain structure of Ni₃Fe alloy upon an A1 → L1₂ phase transition is studied via transmission electron microscopy in combination with the electron backscatter diffraction. It is established that the formation of fresh grain boundaries of general and special types occurs, with the proportion of special-type grain boundaries in the grain boundary ensemble growing. The spectrum of the special grain boundaries changes, due to an increase of the proportion of grain boundaries Σ3 and Σ9. This strengthens the texture of the long-range ordered alloy.     

The effect of antiphase domains on the energy spectra of special boundaries in alloys with the <Emphasis Type="Italic">L</Emphasis>1<Subscript>2</Subscript> superstructure

The special grain boundaries in ordering alloys with the L1₂ superstructure have been investigated by optical metallography and transmission diffraction electron microscopy. The relative energy of the boundaries Σ3 and Σ9 in Ni₃Fe alloy with a short-range order is determined. The energy of these boundaries in an alloy with long-range order is estimated. The energy of twin grain boundaries increases at the phase transitions A1 → L1₂ due to the formation of antiphase grain boundaries in those boundaries. The spectra of special boundaries over Σ and their distributions, depending on the relative energy, change as well. The average relative energy of special grain boundaries in alloys with the L1₂ superstructure increases with increasing the energy of antiphase boundaries.     

Effect of microstructure on fracture in age hardenable Al alloys

ABSTRACT

In the present study, the fracture behaviour of AA6016 alloy was investigated during bending deformation. Wrap-bend tests were conducted and the material was subjected to different bend angles to study crack propagation. The average grain size of the as-received material is approximately 45?μm. The aspect ratio of the grains was changed from 0.53 to 0.40 during bending. The presence of deformation bands was observed during bending in both tensile and compressive regions of the sample. No orientation correlation was observed between the deformation band and its corresponding parent grain. The Schmid factor inside the deformation bands was higher than that of the parent grain, which indicates that the deformation bands accommodate strain during bending. The crystallographic texture evolved significantly during bending deformation. The strength of cube texture component decreases with increasing bend angle and new texture components formed during bending. These new texture components favour either single slip or duplex slip. A mixture of intra-granular and inter-granular fracture occurs during bending. It is observed that inter-granular crack propagation is predominantly favoured along high-angle boundaries, and grain boundary de-cohesion occurs in regions where the misorientation angle is greater than 40°. The formation of deformation-induced coincidence lattice site (CSL) boundaries is also observed during bending and it is shown that the volume fraction of CSL boundaries of Σ3 type increases with increasing bend angle. The current study shows that the formation of deformation-induced CSL boundaries of Σ3 type in AA6016 alloy can improve its inherent resistance to crack propagation during bending.     

Ionic conduction mechanism and relaxation studies of NaNbAlP<Subscript>3</Subscript>O<Subscript>12</Subscript> compound

The Na superionic conductor (NASICON) NaNbAlP₃O₁₂ compound was prepared by the conventional solid-state reaction method. The formation of single-phase material was confirmed by X-ray diffraction studies, and it was found to be a hexagonal phase at room temperature. The electrical conductivity was measured in the frequency range from 200 Hz to 5 MHz and temperatures between 573 and 773 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The analysis of Nyquist plots has revealed the contribution of three electrically active regions corresponding to the bulk mechanism, distribution of grain boundaries, and electrode processes. Besides, the frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. Temperature dependence of the power law exponent s strongly suggests that the non-overlapping small polaron tunneling (NSPT) model is the dominant transport process. The variation of the imaginary part of the complex modulus as a function of angular frequency at several temperatures shows a double relaxation peak suggesting the presence of grains and grain boundaries in the sample. An analysis of the dielectric constants ε″ and loss tangent tan (δ) with frequency shows a distribution of relaxation times.     

The low-temperature minimum of the resistivity of La<Subscript>0.85</Subscript>Ag<Subscript>0.15</Subscript>MnO<Subscript>3</Subscript> manganite

The low-temperature minimum of the La_0.85Ag_0.15MnO₃ resistivity has been investigated. The analysis of the experimental data shows that this minimum of resistivity in zero magnetic field and the large magnetoresistive effect, which increases with a decrease in temperature, can be explained within the model of spin-polarized tunneling of carriers through grain boundaries.     

低温生长Cu(InGa)Se2薄膜吸收层的掺钠工艺研究

在柔性聚酰亚胺衬底上低温制备Cu(In,Ga)Se₂薄膜太阳能电池, Na的掺入会改善电池特性, 但不同的掺Na工艺对Cu(In,Ga)Se₂薄膜和器件特性的改善机理不同. 本实验通过对比前掺NaF和后掺NaF工艺发现, 在前掺Na工艺下, 由于Na始终存在于Cu(In,Ga)Se₂薄膜生长过程中, Na存在于多晶 Cu(In,Ga)Se₂ 薄膜晶界处, 起到了扩散势垒的作用, 导致晶粒细碎、加剧两相分离, 同时减小了施主缺陷的形成概率; 而在后掺Na工艺下, 掺入的Na对薄膜的结构及生长不产生影响, 仅仅起到了钝化施主缺陷、改善薄膜缺陷态的作用. 同时, 研究表明, 后掺Na工艺中, NaF必须依靠外界能量辅助才能扩散进Cu(In,Ga)Se₂内部, 实验结果证实, 只有衬底温度达到350 ℃以上时, 掺入的NaF才能较好地改善薄膜特性. 最终经掺Na工艺的优化, 得到低温工艺制备的柔性聚酰亚胺衬底器件效率达10.4%.     

Transformations in the Grain Boundary Ensemble of M1 Copper Subjected to Equal-Channel Angular Pressing during Recrystallization Annealing

The grain structure of M1 copper subjected to equal-channel angular pressing (ECAP) and subsequent annealing at 593K for 1 h is studied by means of transmission electron microscopy and scanning electron microscopy with the diffraction of backscattered electrons. An increase in grain size and the formation of special boundaries (Σ3 twins both coherent and incoherent) are observed, along with the migration of high-energy Σ3 twins and common grain boundaries, the splitting of Σ9 special boundaries into Σ3 twins, and the splitting of common grain boundaries into Σ9 and Σ3 special boundaries. The local transformation of common grain boundaries into special boundaries also occurs. Particles of the Cu₂O phase are present on the migrating Σ3 twins and common grain boundaries.     

Atomic and electronic structures of a grain boundary in iron with impurity segregation

We present a short review on our current investigations of the atomic and electronic structures of a grain boundary in iron. Atomic structures of grain boundaries were simulated and the local electronic densities of states were calculated in the simulated structure. When phosphorus impurity atoms segregated at the grain boundaries in iron, trigonal prismatic FeP clusters were formed. Segregated boron atoms tended to stay at the central site of polyhedra constructed by host atoms in the grain boundaries. The non-bonding states of the iron atom at the grain boundary disappear by forming a strong bonding orbital with the orbital of the segregated impurity atom. This bonding orbital is formed in a Fe3d host band in the case of a boron impurity. On the other hand, the bonding orbital is formed at lower energies for the phosphorus impurity and is less-mixed with the Fe3d host band. Non-bonding states are formed around the Fe₉P clusters. These can give a qualitative explanation for the embrittlement of the impurity segregated grain boundary. Finally, we can explain from the viewpoint of the electronic structure why the interstitial impurity is the only cohesive enhancer.     

Study of microstructured indium oxide by cathodoluminescence and XPS microscopy

In this work sintered thick microcrystalline films as well as micro and nanostructures of In₂O₃ have been studied. The results obtained by XPS microscopy show that the boundary regions of the microcrystalline films present a higher amount of oxygen, as well as a different O (1s) core level XPS spectrum with respect to the grains. CL images recorded at room temperature show that the emission is preferentially associated with the grain boundaries and the main emission band appeared at 1.9 eV in the recorded CL spectra.Core level and valence band spectromicroscopy measurements of the indium oxide arrows grown at the surface of the sintered InN revealed the incorporation of nitrogen, coming from the starting material. In these structures the N (1s) core level splits into two components, showing a higher amount of nitrogen in the pyramid surface than in the columns of the structures which correlates with an increase of CL intensity.     

Study of resonant tunneling in Au nanoclusters on the surface of SiO2/Si thin films using the combined scanning tunneling microscopy and atomic-force microscopy technique

The morphology and electronic properties of Au nanoclusters on the surface of SiO₂ thin films on n ⁺-Si substrates are studied using the combined scanning tunneling microscopy (STM) and atomic-force microscopy (AFM) technique. The peaks associated with the resonant tunneling of electrons from the states of the valence band of the probe material to the states of the conduction band of the substrate material through Au nanoclusters are observed on the current-voltage characteristics for the contact of a p ⁺-Si AFM probe with Au nanoclusters. Experimental results are interpreted by calculating the tunnel transparency of the SiO₂/Au/SiO₂ double barrier structure in a strong electric field.     

Influence of the modulating interfacial state on Sr2FeMoO6 powder magnetoresistance properties

In this paper, we studied the effects of the modulating interfacial state, which was introduced by mechanical ball milling, on the magnetoresistance (MR) properties of Sr₂FeMoO₆ polycrystalline material. The X-ray diffraction analysis showed that the crystal structure of Sr₂FeMoO₆ polycrystalline material was not changed in the process of ball milling, but the SrMoO₄ impurity phase was introduced at grain boundaries, and its quantity increased with the milling time. The results of resistance measurements at different temperatures indicated that ball milling had a very important influence on the MR properties. At due to the enhancement of the tunneling among adjacent grains by introducing the insulating SrMoO₄ phase at grain boundaries, the MR was enhanced with increasing the milling time. However, at the MR decreased rapidly with the increase in milling time. This phenomenon was mainly caused by the inelastic hopping of electrons through the localized states introduced at grain boundaries.     

Band offsets of epitaxial LaAlO3/TiO2 interface determined by X-ray photoelectron spectroscopy

Room-temperature ferromagnetism in doped anatase TiO₂ has previously been observed, ferromagnetic semiconductor heterostructures based on anatase TiO₂ can thus provide a new opportunity to study spin-dependent transport phenomena at room temperature. An accurate determination of barrier heights or band offsets at the TiO₂-based heterojunctions is of great importance for the spintronics application with semiconductors. X-ray photoelectron spectroscopy with high-energy resolution was used to determine the band offsets of epitaxial LaAlO₃/TiO₂ heterojunction on SrTiO₃(001) substrate fabricated by pulsed laser deposition. Results showed an upward band bending of 0.48(0.03) eV when the film thickness of the overlayer LaAlO₃ above 4 unit cells. The valence band offset obtained is about 0.35(0.16) eV. Assuming bulk band gaps for the LaAlO₃ and TiO₂ epitaxial films, the associated conduction band offset is about 2.95(0.16) eV. These results show that LaAlO₃ can be an ideal tunneling barrier for TiO₂-based heterojunctions.     

An acoustic study of the mixed-alkali-mixed phase β-aluminas. Part 1: Naβ″/βAl2O3, Kβ″/βAl2O3 and (Na0.6K0.4)β″/βAl2O3

The relative attenuation of compressional sound waves of frequencies 10–60 MHz in mixed alkali (Na/K) mixed phase (β″/β)-aluminas is reported for temperatures 80–550 K. The internal friction peaks shift to higher frequencies at higher temperatures and are attributed to Na⁺ interactions in Naβ″/β alumina and Na⁺ and K⁺ in NaK β″/β alumina. The broad attenuation peaks occuring at low temperatures (< 300 K) and at higher temperatures (> 400 K) suggest multi-relaxation processes giving a distribution of activation energies. The estimated average activation energy for Na⁺ diffusion in Naβ″/βAl₂ O₃ at low temperatures and high temperatures is 0.183 eV and 0.387 eV respectively. In the NaK β″/βAl₂o₃ samples, the Na ⁺ values were 0.239 eV and 0.386 eV, respectively. The estimated average activation energies for K⁺ diffusion at low and high temperatures in the Kβ″/β-alumina samples were 0.269 eV and 0.371 eV and for K⁺ in the NaK β″/β samples, 0252 eV and 0.339 eV, respectively. The low temperature attenuation peaks were interpreted in terms of ionic interaction in the bulk and the high temperature peaks were related to interactions in the grain boundaries. The measured activation energies confirmed these interpretations. A reversal of the temperature appearance of the Na⁺ and K⁺ high temperature peaks in the NaKβ″/βAl₂ O₃ is explained by the disorder at the grain boundaries.     

Twin-microstructure enhanced magnetoresistance in La0.67Ba0.33MnO3 oxides

The grain growth dependence of microstructure and its effects on magnetic and transport properties are studied in the polycrystalline La_0.67Ba_0.33MnO₃ oxides. It is found that a lateral growth manner along a certain direction and a concentric terrace pattern along three orthogonal axes occur in the samples sintered at 1573 and 1673 K, respectively. Lamella-like twin microstructure forms in the concentric terrace growth pattern and the magnetoresistance properties can be enhanced by the twin microstructure. It suggests that the twin-boundaries in twin-grains may possibly induce spin-dependent scattering of electrons that is field reduced, or spin-polarized tunneling of electrons that is field enhanced, thus strengthening the effect of grain boundaries.