A crystallographic description of experimentally identified formation reactions of Cu(In,Ga)Se2

This work describes solid-state reactions for the formation of the chalcopyrite compounds CuInSe₂, CuGaSe₂ and Cu(In,Ga)Se₂ on atomic scale. The most important chalcopyrite formation reactions which were identified by the authors by real-time in situ X-ray diffraction in preceding experiments are (A) CuSe+InSe→CuInSe₂, (B) Cu₂Se+2 InSe+Se→2 CuInSe₂ and (C) Cu₂Se+In₂Se₃→2 CuInSe₂. During the selenistaion of a metallic precursor containing gallium a separate fourth reaction occurs: (D) Cu₂Se+Ga₂Se₃→2 CuGaSe₂. The quaternary compound is finally formed by interdiffusion of CuInSe₂ with CuGaSe₂ (E). These five reactions differ in their activation energy and reaction speed. We explain these differences qualitatively by analysing the involved crystal structures for each reaction. It turns out that all reactions involved in the formation of Cu(In,Ga)Se₂ are promoted by epitaxial relations, which facilitates the formation of polycrystalline thin films at temperatures much below those necessary for single crystal growth. Recommendations for the growth of larger grains of Cu(In,Ga)Se₂ containing fewer defects are given.     

Structural investigation of the Cu2Se-In2Se3-Ga2Se3 phase diagram, X-ray photoemission and optical properties of the Cu1−z(In0.5Ga0.5)1+z/3Se2 compounds

Structures of compounds in the Cu₂Se-In₂Se₃-Ga₂Se₃ system have been investigated through X-ray diffraction. Single crystal structure studies for the so-called stoichiometric compounds Cu(In,Ga)Se₂ (CIGSe) confirm that the chalcopyrite structure (space group I4¯2d) is very flexible and can adapt itself to the substitution of Ga for In. On the other hand a structure modification is evidenced in the Cu_1−z(In_0.5Ga_0.5)_1+z/3Se₂ series when the copper vacancy ratio (z) increases; the chalcopyrite structure turns to a modified-stannite structure (I4¯2m) when z≥0.26. There is a continuous evolution of the structure from Cu_0.74(In_0.5Ga_0.5)_1.09Se₂ to Cu_0.25(In_0.5Ga_0.5)_1.25Se₂ ((i.e. Cu(In_0.5Ga_0.5)₅Se₈), including Cu_0.4(In_0.5Ga_0.5)_1.2Se₂ (i.e. Cu(In_0.5Ga_0.5)₃Se₅). From this single crystal structural investigation, it is definitively clear that no ordered vacancy compound exists in that series. X-ray photoemission spectroscopy study shows for the first time that the surface of powdered Cu_1−z(In_0.5Ga_0.5)_1+z/3Se₂ compounds (z≠0) is more copper-poor than the bulk. The same result has often been observed on CIGSe thin films material for photovoltaic applications. In addition, optical band gaps of these non-stoichiometric compounds increase from 1.2 to 1.4 eV when z varies from 0 to 0.75.     

Exfoliation methods for compositional and electronic characterization of interfacial Mo(Sex,Sy) in Cu(In,Ga)(Se,S)2 solar cells by X-ray and UV photoelectron spectroscopy

Mo(Se_xS_y) is a transition metal dichalcogenide typically applied as a back contact interlayer in Cu(In,Ga)(Se,S)₂ (CIGSSe) solar cells. Band alignment at the buried Mo/CIGSSe junction mediated by Mo(Se_xS_y) is important for current transport and enables quasi-ohmic behavior between the CIGSSe absorber and the Mo back electrode. Furthermore, the S/(Se + S) ratio is a crucial parameter that determines the height of the valence band offset at the CIGSSe/Mo(Se_xS_y) interface. Because the interlayer is formed during rapid thermal processing, an MoSe₂ or MoS₂ thin film grown on free substrate surfaces will not be representative for a realistic solar cell device. Thus, for fundamental thin-film material analysis, as well as functional characterization and modeling, appropriate preparation and analytical techniques are required in order to prevent artifacts. In principal, the weak van der Waals forces between two-dimensional stacked Mo(Se_xS_y) sheets allow the implementation of exfoliation procedures to generate free Mo(Se_xS_y) surfaces out of CIGSSe solar cell layer stacks. In this article, two different exfoliation-based Mo(Se_x,S_y) preparation methods are investigated and evaluated with respect to subsequent surface analytical characterization by X-ray and ultraviolet photoelectron spectroscopy. A special focus is laid on an artifact-free characterization of chemical and electronical properties of the exposed layers for a number of samples. In a first instance, the compositional Se/S and (Se + S)/Mo ratios at the surface are quantitatively analyzed on the basis of dedicated peak-fitting routines. Artifacts from carbonaceous contamination due to different exfoliation glues can be prevented through a detailed comparative analysis of carbon 1s and KLL Auger peaks. Furthermore, a significant surface band bending is observed that can be reduced by low-energy Ar ion in situ sputtering. A simple model for the sputter removal of a charged surface layer is presented, which allows to approximately calculate the absolute valence band maximum (VBM) positions required for band alignment and numerical device simulations. The presented exfoliation surface analysis methodology is important for the whole CIGS(Se) solar cell community and may be of general interest for emerging applications of further 2D transition metal dichalcogenides as well.     

A comparative evaluation on the anodic behavior of Cu and Ag electrodes in non-aqueous fluoride and fluoroborate media

The voltammetric responses of copper and silver had been extensively studied and compared in a variety of non-aqueous solvents such as acetonitrile (AN), propylene carbonate (PC) and sulfolane containing two different supporting electrolytes namely triethylaminetrishydrogen fluoride (TEA.3HF) and tetrabutylammonium tetrafluoroborate (TBABF₄). The dissolution rate and surface transformation on the electrode surfaces as a result of anodic polarization was investigated using atomic absorption spectroscopy (AAS) and scanning electron microscopy (SEM), respectively. In solvent-free TEA.3HF medium, the copper electrode shows high charge recovery ratio (Q _c/Q _a), and the difference between the initial anodic and cathodic potentials, obtained at a current density of 2 mA cm⁻², is around 0.11 V, suggesting that in this medium, Cu can certainly serve as reference electrode. On the other hand, on Ag electrode, substantial dissolution was observed leading to very high anodic (Q _a) and cathodic (Q _c) charges, and the surface morphology after the cyclic polarization results in roughened surface with large pores. The effects of incorporating AN and water as additives in TEA.3HF on the solubility and stability of these metal fluoride films are also reported. The dissolution pattern and film formation behavior of these two metals in the different solvents containing fluoride and fluoroborate ionic species have several qualitative similarities, as noted from cyclic voltammetry responses and SEM morphology. Anodic dissolution and precipitation process for both Cu and Ag depends significantly on the nature of supporting electrolytes as well as solvents. In AN containing 0.1 M TEA.3HF, the dissolution of Cu and Ag electrodes was very high. Fluoride salts of Cu show lesser solubility than Ag in those solvents, while fluoroborate salts exhibit the reverse trend. The AAS data suggest that for a particular salt, which may be either fluoride or fluoroborate of Cu and Ag, the relative solubility decreases in the order AN > PC > sulfolane.     

离子液体电沉积CuInxGa1-xSe2薄膜

采用循环伏安法(CV)对离子液体Reline中三元CuCl₂+InCl₃+SeCl₄体系和四元CuCl₂+InCl₃+GaCl₃+SeCl₄体系的电化学行为进行了研究。研究表明,In³⁺并入三元CIS(Cu-In-Se)薄膜体系和Ga³⁺并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径：一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu_1.00In_0.78Ga_0.27Se_2.13的薄膜。     

Synthesis and characterization of Cu3Se2 nanofilms by an underpotential deposition based electrochemical codeposition technique

The Cu₃Se₂ nanofilms were synthesized with underpotential deposition based electrochemical codeposition technique for the first time in the literature. The electrochemical behaviors of copper and selenium were investigated in 0.1 M H₂SO₄ on Au electrode. The effects of concentration and scan rate on the electrochemical behavior of selenium were studied. The electrochemical behaviors in underpotential deposition and bulk regions of the Cu-Se system were investigated in acidic solution by cyclic voltammetry and electrolysis techniques. X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman spectroscopy, and ultraviolet and visible absorption spectroscopy techniques were used for characterization of synthesized films. According to the X-ray photoelectron spectroscopy spectrum, Cu/Se ratio was determined to be approximately 3/2. Copper selenide nanofilms are two phases and polycrystalline according to X-ray diffraction. The films mainly formed tetragonal Cu₃Se₂ (umangite mineral structure) structure and the particle size was approximately 45.95 nm. Scanning electron microscopy images showed that Cu₃Se₂ nanofilms consisted of uniform, nano-sizes and two-dimensional. It was found through AFM that the surface roughness of the film was 6.173 nm, with a mean particle size of around 50 nm. Depending on the deposition time, the band gaps of the Cu₃Se₂ films were in the range of 2.86–3.20 eV. Three characteristic vibrational modes belonging to Cu₃Se₂ nanofilms were recorded in the Raman spectrum.     

Photoelectrochemical water splitting using a Cu(In,Ga)Se2 thin film

The effects of surface modification and reaction conditions on the photoelectrochemical properties of polycrystalline Cu(In,Ga)Se₂ (CIGS) thin films for water splitting were studied. CIGS modified with platinum particles (Pt/CIGS) generated a cathodic photocurrent at potentials up to + 0.4 V vs. RHE at pH = 9.5. The photocurrent was stable for 16 h, which resulted in a turnover number of over 500. A CdS-inserted film (Pt/CdS/CIGS) had significantly improved properties compared to Pt/CIGS: a 0.3 V higher onset potential of cathodic photocurrent and a three-fold increase in the quantum efficiency. Our results suggest the feasibility of CIGS as a photocathode for biphotoelectrochemical water splitting.     

Application of ICP-OES to the determination of CuIn<Subscript>1−x</Subscript>Ga<Subscript>x</Subscript>Se<Subscript>2</Subscript> thin films used as absorber materials in solar cell devices

CuIn_1–xGa_xSe₂ [CIGS; x=Ga/(In+Ga)] thin films are among of the best candidates as absorber materials for solar cell applications. The material quality and main properties of the polycrystalline absorber layer are critically influenced by deviations in the stoichiometry, particularly in the Cu/(In+Ga) atomic ratio. In this work a simple, sensitive and accurate method has been developed for the quantitative determination of these thin films by inductively coupled plasma optical emission spectrometry (ICP-OES). The proposed method involves an acid digestion of the samples to achieve the complete solubilization of CIGS, followed by the analytical determination by ICP-OES. A digestion procedure with 50% HNO₃ alone or in the presence of 10% HCl was performed to dissolve those thin films deposited on glass or Mo-coated glass substrates, respectively. Two analytical lines were selected for each element (Cu 324.754 and 327.396 nm, Ga 294.364 and 417.206 nm, In 303.936 and 325.609 nm, Se 196.090 and 203.985 nm, and Mo 202.030 and 379.825 nm) and a study of spectral interferences was performed which showed them to be suitable, since they offered a high sensitivity and no significant inter-element interferences were detected. Detection limits for all elements at the selected lines were found to be appropriate for this kind of application, and the relative standard deviations were lower than 1.5% for all elements with the exception of Se (about 5%). The Cu/(In+Ga) atomic ratios obtained from the application of this method to CIGS thin films were consistent with the study of the structural and morphological properties by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

离子液体电沉积CuIn_xGa_(1-x)Se_2薄膜(英文)

采用循环伏安法(CV)对离子液体Reline中三元CuCl2+InCl3+SeCl4体系和四元CuCl2+InCl3+GaCl3+SeCl4体系的电化学行为进行了研究。研究表明,In3+并入三元CIS(Cu-In-Se)薄膜体系和Ga3+并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径:一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu1.00In0.78Ga0.27Se2.13的薄膜。     

[Ga(en)3][Ga3Se7(en)] · H2O: Ein Galliumchalkogenid mit Ketten aus [Ga3Se6Se2/2(en)]3–-Bicyclen

[Ga(en)₃][Ga₃Se₇(en)] · H₂O: A Gallium Chalcogenide with Chains of [Ga₃Se₆Se_2/2(en)]^3– Bicycles The new selenidogallate [Ga(en)₃][Ga₃Se₇(en)] · H₂O ( I ) was produced from a ethylendiamine suspension of Ga and Se at 130 °C. I crystallizes in the orthorhombic space group Pna2₁ with unit constants a = 1347.9(3) pm, b = 961.6(1) pm, c = 1967.6(4) pm and Z = 4. The crystal structure contains an anion so far not observed in gallium chalcogenides. It is built from [Ga₃Se₆Se_2/2(en)]^3– bicycles of three Ga^IIIL₄ tetrahedra (L = en, Se) connected via selenium corners to linear chains. The cations, Ga^III ions coordinated by three ethylendiamine in a distorted octahedral geometry are positioned in the holes of the hexagonal rod packing of these chains.     

Impact of thiourea concentration on the properties of sol–gel derived Zn(O,S) thin films and Cu(In,Ga)Se<Subscript>2</Subscript> solar cells

A novel approach based on sol–gel spin coating method to deposit Zn(O,S) thin film using thiourea(TU) as a sulfur source replacing CdS as buffer layer was developed and the influence of TU concentration on the properties of Zn(O,S) thin films and Cu(In,Ga)Se₂(CIGS) solar cells were investigated in this paper. It was found by X-ray diffraction and X-ray photoelectron spectroscopy that sol–gel derived Zn(O,S) thin films were amorphous and composed of ZnS, ZnO as well as Zn(OH)₂. The variation of the optical band gap as a function of the S/(S+O) ratio was determined by energy-dispersive spectroscopy and UV-VIS-NIR. The results indicated that the minimum value for band gap of approximate 3.72?eV was obtained when the S/(S+O)?=?0.44. Efficiency of up to 7.28% was achieved for a CIGS solar cell with Zn(O,S) buffer layer from 0.2M TU, which was attributed to the optimized conduction band offset (CBO) of +0.45?eV at the CIGS/Zn(O,S) interface.

Open image in new window

Zn(O,S) thin films prepared in sol–gel route was used to replace traditional CdS buffer layer deposited by chemical bath deposition method in Cu(In,Ga)Se₂ solar cells. The best efficiency was achieved for CIGS/Zn(O,S)/i-ZnO/ITO heterostructure solar cell with S/(S+O)?=?0.18, which was attributed to the optimized conduction band offset (CBO) of +0.45?eV at the CIGS/Zn(O,S) interface.

     

Bis­[bis(N,N‐diethyl‐1,1‐di­seleno­car­bam­ato)copper(II)], [Cu(Se2CNEt2)2]2

The title centrosymmetric Cu^II binuclear complex, bis(μ‐N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′:Se)­bis­[(N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′)copper(II)], [Cu(Se₂CNEt₂)₂]₂ or [Cu₂(C₅H₁₀NSe₂)₄], is built from two symmetry‐related [Cu{Se₂CN(Et)₂}₂] units by pairs of Cu—Se bonds. The coordination geometry at the unique Cu atom is distorted square pyramidal, with Cu—Se distances in the range 2.4091 (11)—2.9095 (10) Å.     

Protein‐Directed Solution‐Phase Green Synthesis of BSA‐Conjugated MxSey (M=Ag,Cd, Pb,Cu) Nanomaterials

Bovine serum albumin (BSA)‐conjugated M_xSe_y (M=Ag, Cd, Pb, Cu) nanomaterials with different shapes and sizes were synthesized in water at room temperature by a protein‐directed, solution‐phase, green synthetic method. The method features very low energy consumption and nontoxic reagents with high yields of concentrated nanoparticles. The obtained bioconjugated nanoparticles have good dispersibility, bioactivity, and biocompatibility. In addition, various functional groups of protein on the surface of the nanocrystals are suitable for further biological interactions or couplings, which is very important for further biological applications.     

Synthesis, electrical properties, and structural features of copper-containing chalcogenide films produced by the chemical deposition method

Multicomponent copper-containing CuI-AsI₃-As₂Se₃ and CuI-Sb₃I-As₂Se₃ chalcogenide films were produced by chemical deposition from solutions of chalcogenide glasses in n-butylamine and their electrical conductivity was studied. It was shown that the electrical properties of chalcogenide glasses and films based on these glasses have the same values within experimental error. It was found sing Mossbauer spectroscopy that antimony atoms are in the Sb(III) state in the environment of three selenium atoms, and copper ions in the Cu(I) state and are surrounded by iodine atoms. The chalcogenide films can be used to fabricate ion-selective electrodes sensitive to copper cations.     

非水体系中苯并三唑在铜电极上吸附的电化学表面增强拉曼光谱研究

采用电化学现场表面增强拉曼光谱(SERS)研究了非水体系中苯并三唑(BTAH)在铜电极上的吸附及成膜行为, 结果表明非水体系中BTAH的吸附行为随电位变化而不同. 较负电位区间主要以中性分子形式吸附; 中间电位区间主要以BTA^－吸附并不可逆成膜; 而在氧化电位区间主要表现为铜的氧化. 随中性配体三苯基膦(pph₃)的加入, 在中间电位区间, 由于易溶的Cu(pph₃)_n⁺的生成而使铜的溶解速度加快, 最终该阳离子在溶液中和BTA^-作用而生成了多核铜的配合物. 采用直接电化学方法模拟电极表面过程合成了相应的吸附产物, 并对其组成进行了相关表征.     

Reaktionen der Digalliumverbindung R2Ga–GaR2 [R = CH(SiMe3)2] mit Wasser und Carbonsäuren – Synthese von μ‐Hydroxo‐μ‐carboxylatodigallium‐Verbindungen unter Erhalt der Ga–Ga‐Bindungen

Treatment of the digallium compound R₂Ga–GaR₂ [ 1 , R = CH(SiMe₃)₂] with a broad variety of functionalized carboxylic acids in the presence of water yielded μ‐hydroxo‐μ‐carboxylatodigallium compounds ( 2 – 10 ) containing intact Ga–Ga bonds in high to moderate yields. The compounds form dimeric formula units in which the unsupported Ga–Ga bonds are bridged by two hydroxo and two carboxylato ligands. Each gallium atom is terminally coordinated by a bulky alkyl group. NMR spectroscopy revealed mixtures of two isomeric compounds in solution in all cases. The second component may show a different bridging mode with each Ga–Ga bond bridged by a bidentate carboxylato ligand to form Ga₂O₂C five‐membered heterocycles.     

Tyrrellite,Cu(Co0.68Ni0.32)2Se4, isostructural with spinel

Tyrrellite, a naturally occurring Co–Ni–Cu selenide, has been studied by single‐crystal X‐ray diffraction. It possesses the normal spinel‐type structure, with Cu occupying the tetrahedral site and (Co+Ni) the octahedral site. The average Cu—Se distance of 2.3688 (2) Å is close to that of 2.3703 (8) Å in CuCr₂Se₄, whereas the average (Co+Ni)—Se distance of 2.3840 (1) Å appears to be slightly shorter than most octahedral Co—Se or Ni—Se distances (∼2.40–2.50 Å) in other selenides. The refined structure provides a basis for a redefinition of the ideal chemical formula of tyrrellite, which should be Cu(Co,Ni)₂Se₄, rather than the previously suggested (Cu,Co,Ni)₃Se₄.     

拓扑绝缘体二维纳米结构与器件

拓扑绝缘体是一种全新的量子功能材料, 具有绝缘性体能带结构和受时间反演对称性保护的自旋分辨的金属表面态, 属于Dirac 粒子系统, 将在新原理纳电子器件、自旋器件、量子计算、表面催化和清洁能源等方面有广泛的应用前景. 理论和实验相继证实Sb₂Te₃, Bi₂Se₃和Bi₂Te₃单晶具有较大的体能隙和单一Dirac 锥表面态, 已经迅速成为了拓扑绝缘体研究中的热点材料. 然而, 利用传统的高温烧结法所制成的拓扑绝缘体单晶块体样品常存在大量本征缺陷并被严重掺杂, 拓扑表面态的新奇性质很容易被体载流子掩盖. 拓扑绝缘体二维纳米结构具有超高比表面积和能带结构的可调控性, 能显著降低体态载流子的比例和凸显拓扑表面态, 并易于制备高结晶质量的单晶样品, 各种低维异质结构以及平面器件. 近年来, 我们一直致力于发展拓扑绝缘体二维纳米结构的控制生长方法和物性研究. 我们发展了拓扑绝缘体二维纳米结构的范德华外延方法, 实现了高质量大比表面积的拓扑绝缘体二维纳米结构的可控制备, 并实现了定点与定向的表面生长. 开展拓扑绝缘体二维纳米结构的谱学研究, 利用角分辨光电子能谱直接观察到拓扑绝缘体狄拉克锥形的表面电子能带结构, 发现了拉曼强度与位移随层数的依赖关系. 设计并构建拓扑绝缘体纳米结构器件, 系统研究其新奇物性, 观测到拓扑绝缘体Bi₂Se₃表面态的Aharonov-Bohm (AB)量子干涉效应等新奇量子现象, 通过栅电压实现了拓扑绝缘体纳米薄片化学势的调控, 并将拓扑绝缘体纳米结构应用于柔性透明导电薄膜. 本文首先简单介绍拓扑绝缘体的发展现状, 然后系统介绍我们开展的拓扑绝缘体二维纳米结构的范德华外延生长、谱学、电学输运特性以及透明柔性导电薄膜应用的研究, 最后对该领域所面临的机遇和挑战进行简要的展望.     

Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: A new one-dimensional indium selenide

A new organically templated indium selenide, [C₆H₁₆N₂][In₂Se₃(Se₂)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV-vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C₆H₁₆N₂][In₂Se₃(Se₂)] contains anionic chains of stoichiometry [In₂Se₃(Se₂)]²⁻, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In₂Se₃(Se₂)]²⁻ chains, which consist of alternating four-membered [In₂Se₂] and five-membered [In₂Se₃] rings, contain perselenide (Se₂)²⁻ units. UV-vis diffuse reflectance spectroscopy indicates that [C₆H₁₆N₂][In₂Se₃(Se₂)] has a band gap of 2.23(1) eV.     

Thermal decomposition of basic copper sulphate monohydrate

The thermal decomposition of copper sulphate hydroxide hydrate, (CuO·CuSO₄). 2Cu(OH)₂·H₂O, to copper oxysulphate and CuO was investigated by X-ray phase analysis, IR spectroscopy, complex thermal analysis and electron microscopy. The effect of water vapour and time of treatment on the formation of decomposition products with a large surface area is studied. The strong decrease in specific surface area of the precipitate (from 80 m²/g to 20 m²/g) thermally treated at a temperature above 250°C is associated with the elimination of water having a coordination bond with the Cu²⁺ ion. During this process, the interplanar distances of the crystal lattice of copper sulphate hydroxide hydrate decrease. The time of decomposition of this compound essentially affects the decrease of the specific surface area. When the decomposition proceeds in an atmosphere containing water vapour sintering processes are predominating and the phase obtained has a considerably smaller specific surface area than in cases of decomposition under dry air.