A non-selenization technology by co-sputtering deposition for solar cell applications

This work presents a novel method to form polycrystalline Cu(In(1-x)Ga(x))Se(2) (CIGS) thin film by co-sputtering of In─Se and Cu─Ga alloy targets without an additional selenization process. An attempt was also made to thoroughly elucidate the surface morphology, crystalline phases, physical properties, and chemical properties of the CIGS films by using material analysis methods. Experimental results indicate that CIGS thin films featured densely packed grains and chalcopyrite phase peaks of (112), (220), (204), (312), and (116). Raman spectroscopy analysis revealed chalcopyrite CIGS phase with Raman shift at 175 cm(-1), while no signal at 258 cm(-1) indicated the exclusion of Cu(2-x)Se phase. Hall effect measurements confirmed the polycrystalline Cu(In,Ga)Se₂ thin film to be of p type semiconductor with a film resistivity and mobility of 2.19×10(2) Ω cm and 88 cm(2)/V s, respectively.     

Grain boundaries in Cu(In,?Ga)(Se,?S)2 thin-film solar cells

The paper reviews the current status of the research on grain boundaries in polycrystalline Cu(In, Ga)(S, Se)₂ alloys used as absorber materials for thin-film solar cells. We discuss the different concepts that are available to explain the relatively low electronic activity of grain boundaries in these materials. Numerical simulations that have been undergone so far to model the polycrystalline solar cells are briefly summarized. In addition, we give an overview on the experiments that have been conducted so far to elucidate the structural, defect-chemical, and electronic properties of grain boundaries in Cu(In, Ga)(S, Se)₂ thin-films.     

Direct insight into grain boundary reconstruction in polycrystalline Cu(In,Ga)SE2 with atomic resolution

This work presents results from high-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy on twin boundaries (TBs) and nontwin grain boundaries (GBs) in Cu(In,Ga)Se(2) thin films. It is shown that the atomic reconstruction is different for different symmetries of the grain boundaries. We are able to confirm the model proposed by Persson and Zunger [Phys. Rev. Lett. 91, 266401 (2003)] for Se-Se-terminated Σ3 {112} TBs, showing Cu depletion and In enrichment in the two atomic planes closest to the TB. On the contrary, Cu depletion without In enrichment is detected for a cation-Se-terminated TB. At nontwin GBs, always a strong anticorrelation of Cu and In signals is detected suggesting that the formation of In(Cu) or Cu(In) antisites within a very confined region of smaller than 1 nm is an essential element in the reconstruction of these GBs.     

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     

Growth mechanism of thermally processed Cu(In,Ga)S2 precursors for printed Cu(In,Ga)(S,Se)2 solar cells

We investigate a process used for the selenisation of particle‐based precursors to prepare low‐cost Cu(In,Ga)(S,Se)₂ (CIGS) solar cells. It is suitable for high throughput with a short optimum selenisation duration of 3–5 min and employs a rapid thermal annealing system with elemental selenium vapour. Homogeneous crack‐free Cu(In,Ga)S₂ precursor films of up to 1 µm are obtained via doctor blading. The high selenium vapour pressure in the selenisation reaction chamber results in the formation of a compact Cu(In,Ga)(S,Se)₂ layer on top of a carbon‐rich underlayer. In order to investigate the phase development in the film, the selenisation process was interrupted at different stages and the samples were monitored via XRD and surface‐sensitive Raman measurements. We find the formation of a polycrystalline Cu(In,Ga)Se₂ phase already after 1 s at the target temperature of 550 °C. Furthermore, the effect of initial precursor thickness on solar cell parameters is discussed. Complete solar cells are prepared by conventional methods, leading to conversion efficiencies well above 8%. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Doping dependent evolution of magnetism and superconductivity in Eu(1-x)K(x)Fe2As2 (x = 0-1) and temperature dependence of the lower critical field H(c1)

We have synthesized polycrystalline samples of Eu(1-x)K(x)Fe2As2 (x = 0-1) and carried out systematic characterization using x-ray diffraction, ac and dc magnetic susceptibility, and electrical resistivity measurements. A clear signature of the coexistence of a superconducting transition (T(c) = 5.5 K) with spin density wave (SDW) ordering is observed in our underdoped sample with x = 0.15. The SDW transition disappears completely for the x = 0.3 sample and superconductivity arises below 20 K. The superconducting transition temperature Tc increases with increase in the K content and a maximum Tc = 33 K is reached for x = 0.5, beyond which it decreases again. The doping dependent Tx phase diagram is extracted from the magnetic and electrical transport data. It is found that magnetic ordering of Eu moments coexists with the superconductivity up to x = 0.6. The isothermal magnetization data taken at 2 K for the doped samples suggest the 2+ valence state of the Eu ions. We also present the temperature dependence of the lower critical field H(c1) of the superconducting polycrystalline samples. The values of H(c1)(0) obtained for x = 0.3, 0.5, and 0.7 after taking the demagnetization factor into account are 202, 330, and 212 Oe, respectively. The London penetration depth λ(T) calculated from the lower critical field does not show exponential dependence at low temperature, as would be expected for a fully gapped clean s-wave superconductor. In contrast, it shows a T2 power law feature up to T = 0.3Tc, as observed in Ba(1-x)K(x)Fe2As2 and BaFe(2-x)Co(x)As2.     

Site Preference of Se and Te in Bi_2Se_(3-x)Te_x Thin Films

The ternary topological insulators Bi₂Se_3-xTe_x have attracted a great deal of attention due to their exotic physical and chemical properties.While most of the studies focus on the properties of these ternary TIs,limited research was performed to investigate the dynamic atomic stack of its crystal structure.We prepared highquality Bi₂Se_3-xTe_x thin films on Ga As(111)B substrates using molecular beam epitaxy,characterized with Raman...     

Nanocrystalline versus microcrystalline Li(2)O:B(2)O3 composites: anomalous ionic conductivities and percolation theory

We study ionic transport in nano- and microcrystalline (1-x)Li(2)O:xB(2)O3 composites using standard impedance spectroscopy. In the nanocrystalline samples (average grain size of about 20 nm), the ionic conductivity sigma(dc) increases with increasing content x of B2O3 up to a maximum at x approximately 0.5. Above x approximately 0.92, sigma(dc) vanishes. By contrast, in the microcrystalline samples (grain size about 10 &mgr;m), sigma(dc) decreases monotonically with x and vanishes above x approximately 0. 55. We can explain this strikingly different behavior by a percolation model that assumes an enhanced conductivity at the interfaces between insulating and conducting phases in both materials and explicitly takes into account the different grain sizes.     

LED用荧光粉Sr（S1-xSex）：Eu^2＋的合成和光谱性质研究

采用高温固相法合成了Sr(S1-xSex)系列硫属化合物掺Eu2 荧光粉.XRD表明荧光粉的组成为单相,而且体系Sr(Sl-xSex):0.005Eu2 中晶胞参数随着组成的变化呈现良好的线性关系,遵守韦加定律.漫反射光谱与激发光谱吻合,说明荧光粉吸收的能量能够有效地激发发光中心而发光,激发光谱中较低能量区域覆盖了400～500 nm的光谱范围,与蓝光LED芯片的发射光匹配.发射光谱呈现的是Eu2 离子的5d→4f特征跃迁发射带,当x由0增加到1.0的过程中,发射峰值波长由617 nm逐渐蓝移到571 nm.不同基质中掺杂的Eu2 离子的荧光寿命均为微秒数量级,与Eu2 离子的4f65d1→4f7跃迁相符合.将荧光粉封装在发蓝色光(λ=460 nm)的GaN芯片上制作了LED器件,测量了器件的发光强度、色纯度和色坐标等参数.Sr(S1-xSex):Eu2 系列硫属化合物掺铕荧光粉能够有效地被GaN芯片发出的蓝色光激发,发出从橙色到红色的可见光,是一类较好的LED用荧光粉.     

Local current–voltage behaviors of preferentially and randomly textured Cu(In,Ga)Se2 thin films investigated by conductive atomic force microscopy

Electrical transport properties on polycrystalline Cu(In,Ga)Se₂ (CIGS) (Ga/(In+Ga) ≈35%) thin films were examined by conductive atomic force microscopy. The CIGS thin films with a (112) preferential or random texture were deposited on Mo-coated glass substrates. Triangular pyramidal grain growths were observed in the CIGS thin films preferentially textured to the (112) planes. Current maps of the CIGS surface were acquired with a zero or non-zero external voltage bias. The contrast of the images on the grain boundaries and intragrains displayed the conduction path in the materials. Local current–voltage measurements were performed to evaluate the charge conduction properties of the CIGS thin films.     

Spectromicroscopic investigation of (NH4)2S treated polycrystalline Cu(In1−xGax)Se2

Device-grade polycrystalline thin-film Cu(In_1−xGa_x)Se₂ was treated with (NH₄)₂S at 60°C to determine the resulting microscopic surface composition/morphology. Scanning electron microscopy was used to evaluate the resultant macroscopic surface morphology. Modification of the surface and grain boundary chemistry of the Cu(In_1−xGa_x)Se₂ polycrystalline films was investigated with scanning photoemission spectromicroscopy. The submicrometer lateral resolution of this technique allows us to directly characterize not only the surface chemistry of the treated films on the submicron scale, but also to probe the grain boundary chemistry. Chemical maps depicting the distribution of chemical species on the surface and at grain boundaries were obtained by monitoring the S 2p, Se 3d, In 4d/Ga 3d and Cu 3d (valence band) photoelectrons while scanning the sample. Background maps were also acquired of each of the peak energies to separate chemical contrast from topographic contrast. Results show that S has been incorporated at the surface, possibly creating a wider bandgap Cu(In_1−xGa_x)(Se_1−yS_y)₂ surface layer, and along the grain boundaries. The purpose of this investigation is to find an environmentally safe replacement for the toxic CdS overlayer commonly used for heterojunction devices without sacrificing overall device performance and reliability.     

Lithium/Silver-Doped Cu_2ZnSnS_4 with Tunable Band Gaps and Phase Structures: a First-Principles Study

Doping is an effective approach for improving the photovoltaic performance of Cu_2 ZnSnS_4(CZTS). The doping by substitution of Cu atoms in CZTS with Li and Ag atoms is investigated using density functional theory. The results show that the band gaps of Li_(2 x)Cu_(2(1-x))ZnSnS_4 and Ag_(2 x)Cu_(2(1-x))ZnSnS4 can be tuned in the ranges of 1.30-3.43 and 1.30-1.63 eV, respectively. The calculation also reveals a phase transition from kesterite to wurtzite-kesterite for Li_(2 x)Cu_(2(1-x))ZnSnS_4 as x is larger than 0.9. The tunable band gaps of Li_(2 x)Cu_(2(1-x))ZnSnS_4 and Ag_(2 x)Cu_(2(1-x)) ZnSnS_4 make them beneficial for achieving band-gap-graded solar cells.     

Room temperature oxidation of Cu(3)Ge films grown on Si and Si(1-x)Ge(x) substrates

Room temperature oxidation of Cu3Ge films grown on Si, Si(0.85)Ge(0.15) and Si(0.52)Ge(0.48) substrates, respectively, at a temperature of 200-300 degrees C was studied using transmission electron microscopy (TEM) in conjunction with energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM). For Cu(3)Ge films grown at 200 degrees C and subsequently exposed in air for 1 week oxide protrusions and oxide networks appeared in the film surface and grain boundaries of Cu(3)Ge, respectively. At room temperature O from air and Si from the substrate, diffused along the grain boundaries of Cu(3)Ge to react with Cu(3)Ge grains, initiating the Cu(3)Si-catalyzed oxidation. Cu(3)Ge films are superior to Cu(3)(Si(1-x)Gex) films in retarding Cu(3)Si-catalyzed oxidation. Annealing at 300 degrees C allowed Si diffusion from the substrate into the Cu(3)Ge overlayer to form Cu(3)(Si(1-x)Gex), enhancing the Cu(3)Si-catalyzed oxidation rate. In the present study, Cu(3)Ge films grown on Si(0.52)Ge(0.48) at 200 degrees C show the best resistance to room temperature oxidation because higher Ge concentration in the substrate and lower temperature annealing can more effectively retard Si diffusion from the substrate into the Cu(3)Ge overlayer, and hence reduce the Cu(3)Si-catalyzed oxidation rate.     

Room-temperature ferromagnetism induced by Cu vacancies in Cu_x(Cu_2O)_(1-x) granular films

Cux(Cu2O)1-x(0.09 x 1.00) granular films with thickness about 280 nm have been fabricated by direct current reactive magnetron sputtering. The atomic ratio x can be controlled by the oxygen flow rate during Cux(Cu2O)1-x deposition. Room-temperature ferromagnetism(FM) is found in all of the samples. The saturated magnetization increases at first and then decreases with the decrease of x. The photoluminescence spectra show that the magnetization is closely correlated with the Cu vacancies in the Cux(Cu2O)1-x granular films. Fundamentally, the FM could be understood by the Stoner model based on the charge transfer mechanism. These results may provide solid evidence and physical insights on the origin of FM in the Cu2O-based oxides diluted magnetic semiconductors, especially for systems without intentional magnetic atom doping.     

Effect of Cu doping on the magnetic and electrical properties of n=2 Ruddlesden-Popper manganates

A series of polycrystalline Cu-doped n=2 Ruddlesden-Popper manganates La1.2Sr1.8CuzMn（2-x）O7 （x=0, 0.04, 0.13） were synthesized by the solid state reaction method. The effect of Cu doping on the magnetic and transport properties has been studied. It is found that Cu substitution for Mn greatly affects the magnetic and electrical properties of the parent phase La1.2Sr1.8Mn2O7. With the increase of Cu content, the system undergoes a transition from longrange ferromagnetic order to the spin glass state and further to an antiferromagnetic order. A little of Cu dopant can lead to the samples showing semiconductor or insulator behaviour in the whole observed temperature range while the parent phase has a metal-insulator transition. These samples show colossal magnetoresistance at low temperatures and the value of it decreases with increasing Cu content.     

Common energy scale for magnetism and superconductivity in underdoped cuprates: a muon spin resonance investigation of (Ca(x)La(1-x)) (Ba(1.75-x)La(0.25+x))Cu3O(y)

We characterize the spontaneous magnetic field, and determine the associated temperature T(g), in the superconducting state of (Ca(x)La(1-x)) (Ba(1.75-x)La(0.25+x)) Cu(3)O(y) using zero and longitudinal field muon spin resonance measurements for various values of x and y. Our major findings are (i) T(g) and T(c) are controlled by the same energy scale, (ii) the phase separation between hole poor and hole rich regions is a microscopic one, and (iii) spontaneous magnetic fields appear gradually with no moment size evolution.     

Enhancements in specimen preparation of Cu(In,Ga)(S,Se)2 thin films

When producing slices from Cu(In,Ga)(S,Se)(2) thin films for solar cells by use of a focused ion beam (FIB), agglomerates form on the Cu(In,Ga)(S,Se)(2) surfaces, which deteriorate substantially the imaging and analysis in scanning electron microscopy. Similar problems are also experienced when depth-profiling Cu(In,Ga)(S,Se)(2) thin films by means of glow-discharge or secondary ion mass spectrometry. The present work shows that the agglomerates are composed of (mainly) Cu, and that their formation may be impeded considerably by either cooling of the sample or by use of reactive gases during the ion-beam sputtering. The introduction of XeF(2) during FIB slicing resulted in excellent images, in which the microstructures of most layers in the Cu(In,Ga)(S,Se)(2) thin film stack are visible, including the microstructure of the 20 nm thin MoSe(2) layer. Acquisition of high-quality two-dimensional and also three-dimensional electron backscatter diffraction data was possible. The present work gives a basis for enhanced SEM imaging and analysis not only in the case of Cu(In,Ga)(S,Se)(2) thin films but also when dealing with further material systems exhibiting similar formations of agglomerates.     

Magnetic properties of hole-doped SCGO, SrCr(8)Ga(4-x)M(x)O(19) (M?=?Zn, Mg, Cu)

We report changes in the magnetic properties of hole-doped SCGO, SrCr8Ga4O19, induced by replacing non-magnetic Ga3+ with both non-magnetic (Mg2+ and Zn2+) and magnetic (Cu2+) cations. The resulting solid solutions, SrCr(8)Ga(4-x)M(x)O(19) (M = Zn, Mg, Cu) have been studied by x-ray diffraction and magnetic susceptibility measurements. For all cases, at least 10% of Ga can be replaced by divalent cations resulting in oxidation of ≥5% of the Cr3+ d3 to Cr4+ (d2). The hole doping results in an increase in ferromagnetic interactions and reduces the magnetic frustration. In the SrCr(8)Ga(4-x)Cu(x)O(19) series an enhancement of the spin-glass-like transition is observed, T(f)～ 6 K, which we ascribe to the magnetic nature of the Cu2+ (d9) dopant.     

Origin of the tunnel anisotropic magnetoresistance in Ga(1-x)Mn(x)As/ZnSe/Ga(1-x)Mn(x)As magnetic tunnel junctions of II-VI/III-V heterostructures

We investigated spin-dependent transport in magnetic tunnel junctions made of III-V Ga(1-x)Mn(x)As electrodes and II-VI ZnSe tunnel barriers. The high tunnel magnetoresistance (TMR) ratio up to 100% we observed indicates high spin polarization at the barrier/electrodes interfaces. We found anisotropic tunneling conductance having a magnitude of 10% with respect to the direction of magnetization to linearly depend on the magnetic anisotropy energy of Ga(1-x)Mn(x)As. This proves that the spin-orbit interactions in the valence band of Ga(1-x)M(x)As are responsible for the tunnel anisotropic magnetoresistance (TAMR) effect.     

Magnetostructural transition in NiCuCoMnGa alloys

The effects of the addition of Co on the martensitic transformation and Curie transition temperatures of polycrystalline Ni46-xCu4CoxMn33.sGa16.5 （x = 0, 1, 3, 5） alloys are investigated. An abrupt decrease in the martensitic transformation temperature and an obvious increase in the Curie transition temperature of austenite （TA） are observed when Co is doped in the NiCuMnGa alloy. As a result, the composition range for obtaining the magnetostructural transition is extended. Furthermore, the effect of a strong magnetic field on the magnetostructural transition is analyzed. This study offers a possible method to extend the composition range for obtaining magnetostructural transition in Heusler alloys.