Scalable fabrication of Bi_2O_2Se polycrystalline thin film for near-infrared optoelectronic devices applications

We present a controlled, stepwise formation of layered semiconductor Bi_2O_2 Se thin films prepared via the vapour process by annealing topological insulator Bi_2Se_3 thin films in low oxygen atmosphere for different reactions. Photodetectors based on Bi_2O_2 Se thin film show a responsivity of 1.7×10~4 A/W at a wavelength of 980 nm. Field-effect transistors based on Bi_2O_2 Se thin film exhibit n-type behavior and present a high electron mobility of 17 cm~2/V·s. In addition, the electrical properties of the devices after 4 months keeping in the air shows little change, implying outstanding air-stability of our Bi_2O_2 Se thin films. From the obtained results, it is evident that low oxygen annealing is a surprisingly effective method to fabricate Bi_2O_2 Se thin films for integrated optoelectronic applications.     

利用Ag_2O/PEDOT:PSS复合缓冲层提高P3HT:PCBM聚合物太阳能电池器件性能的研究

利用Ag2O/PEDOT:PSS(聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸盐)作为复合阳极缓冲层,制备了P3HT:PCBM(聚(3-已基噻吩):富勒烯衍生物)聚合物太阳能电池器件,并通过改变氧化银插入层的厚度来分析复合缓冲层对器件性能的影响.实验发现,具有阳极缓冲层修饰的器件在退火处理后,光伏性能得到了改善.相比于单一PEDOT:PSS缓冲层的器件,Ag2O/PEDOT:PSS复合缓冲层可以增大器件的短路电流密度和外量子效率,使器件效率得到提高.分析表明,退火处理可以有效改善活性层的薄膜形貌,增加光的吸收和激子的解离,而较薄氧化银的引入,可以有效降低阳极处空穴的输运势垒,提高器件空穴收集效率,并能充当化学间隔层,提高器件光伏性能和稳定性.     

具有本征低晶格热导率的硫化银快离子导体的热电性能

硫化银(Ag_2S)是一种典型的快离子导体材料,前期关于Ag_2S的研究主要集中在光电和生物等领域.最近的研究表明, a-Ag_2S具有和金属一样的良好延展性和变形能力.但是, Ag_2S的热电性能尚无公开报道.本工作合成了单相Ag_2S化合物,系统研究了其在300—600 K范围的物相变化、离子迁移特性和电热输运性质.研究发现, Ag_2S在300—600 K温度区间表现出半导体的电输运性质.由于单斜-体心立方相晶体结构转变, Ag_2S的离子电导率、载流子浓度、迁移率、电导率、泽贝克系数等性质在455 K前后出现急剧变化.在550 K, Ag_2S的功率因子最高可达5μW·cm~(–1)·K~(–2). Ag_2S在300—600 K温度区间均表现出本征的低晶格热导率(低于0.6 W·m~(–1)·K~(–1)). S亚晶格中随机分布的类液态Ag离子是导致b-Ag_2S体心立方相具有低晶格热导率的主要原因.在573 K, Ag_2S的热电优值可达0.55,与Ag_2Se, Ag_2Te, CuAgSe等已报道的Ag基快离子导体热电材料的性能相当.     

二硒化铁/还原氧化石墨烯的制备及其在染料敏化太阳能电池中的应用

通过水热反应合成出二硒化铁/还原氧化石墨烯(FeSe₂/rGO)复合材料, 并将其作为对电极材料应用于染料敏化太阳能电池(DSSC). 利用X射线衍射、拉曼光谱、场发射扫描电子显微镜和高分辨透射电子显微镜对FeSe₂/rGO的结构和形貌进行了表征. 利用循环伏安法、电化学阻抗谱和Tafel曲线测试分析了FeSe₂/rGO对电极的电催化活性. 结果表明: FeSe₂呈纳米棒结构, 长度在100-200 nm之间, 且紧密地附着在rGO 的表面, FeSe₂/rGO对电极对I₃^-的还原具有很好的催化活性. 电池的J-V曲线测试显示: 基于FeSe₂/rGO对电极的DSSC的转换效率达到了8.90%, 相比基于单纯的FeSe₂对电极的DSSC(7.91%)和rGO对电极的DSSC(5.24%)都有了显著提高, 甚至优于铂对电极的DSSC(8.52%).     

三氧化钨/氧化银复合材料的水热法合成及其光催化降解性能研究

染料污染是水污染中最严重的问题之一,吸引了很多科学家的关注.人们尝试了很多方法去解决该问题,如化学氧化法、物理吸附法、光催化降解法和生物降解法等.与其他几种方法相比,光催化法有着低能耗、环保以及高效等优势.三氧化钨是常见的半导体材料,具有独特的光学性能,近年来受到了广泛的研究.本文以钨酸钠和硫脲为前驱体,通过水热法制备了三氧化钨/氧化银(WO_3/Ag_2O)复合材料,并用光催化降解亚甲基蓝来分析其光催化性能.通过X射线光电子能谱、X射线衍射、透射电子显微镜、扫描电子显微镜、紫外可见吸收光谱等表征手段对样品的形貌、晶格结构和光催化的性能进行表征.氧化银的带宽为1.2 e V,对可见光很敏感,三氧化钨和氧化银的复合使材料在可见光下的光催化活性显著增强,在可见光下对亚甲基蓝染料的光降解率可以达到98%.实验结果表明,复合材料中的三氧化钨纳米棒为六方相,其平均直径约为200 nm,平均长度约为4μm.而复合材料中的氧化银纳米颗粒为六方相,附着在氧化钨纳米棒的表面,平均晶粒尺寸为20 nm.氧化银的存在为复合材料提供了更多的反应活性位点.相较于单一组分,复合材料在可见光下的光吸收度更高,这说明三氧化钨和氧化银的复合改变了材料的能带结构.研究发现,三氧化钨和氧化银之间形成的异质结构是其优良光催化性能的来源.此外,三氧化钨和氧化银复合材料还具有良好的催化稳定性和化学稳定性.本文结果表明,可以通过给宽带隙的半导体材料复合一些带隙合适的金属氧化物以提升其光催化活性.     

Photoelectrochemical activity of ZnO:Ag/rGO photo-anodes synthesized by two-steps sol-gel method

This work investigated the influence of silver plasmon and reduced graphene oxide (rGO) on the photoelectrochemical performance (PEC) of ZnO thin films synthesized by the sol-gel method. The physicochemical properties of the obtained photo-anodes were systematically studied by using several characterization techniques. The x-ray diffraction analysis showed that all samples presented hexagonal wurtzite structure with a polycrystalline nature. Raman and energy dispersive x-ray (EDX) studies confirmed the existence of both Ag and rGO in ZnO:Ag/rGO thin films. The estimated grain size obtained from scanning electron microscopy (SEM) analysis decreased with Ag doping, then increased to a maximum value after rGO addition. The UV-vis transmission spectra of the as-prepared ZnO:Ag and ZnO:Ag/rGO thin films have shown a reduction in the visible range with a redshift at the absorption edges. The bandgaps were estimated to be around 3.17 eV, 2.7 eV, and 2.52 eV for ZnO, ZnO:Ag, and ZnO:Ag/rGO, respectively. Moreover, the electrical measurements revealed that the charge exchange processes were enhanced at the ZnO:Ag/rGO/electrolyte interface, accompanied by an increase in the (PEC) performance compared to ZnO and ZnO:Ag photo-anodes. Consequently, the photocurrent density of ZnO:Ag/rGO (0.2 mA·cm^-2) was around 4 and 2.22 times higher than photo-anodes based on undoped ZnO (0.05 mA·cm^-2) and ZnO:Ag (0.09 mA·cm^-2), respectively. Finally, from the flat band potential and donor density, deduced from the Mott-Schottky, it was clear that all the samples were n-type semiconductors with the highest carrier density for the ZnO:Ag/rGO photo-anode.     

Enhancing the thermoelectric performance through the mutual interaction between conjugated polyelectrolytes and single-walled carbon nanotubes

We present a method of constructing composites composed of conjugated polyelectrolytes(CPEs)and singlewalled carbon nanotubes(SWCNTs)to obtain a high-performing flexible thermoelectric generator.In this approach,three kinds of polymers,namely,poly[(1,4-(2,5-didodecyloxybenzene)-alt-2,5-thiophene](P1),poly[(1,4-(2,5-bis-sodium butoxysulfonate-phenylene)-alt-2,5-thiophene](P2),and poly[(1,4-(2,5-bis-acid butoxysulfonic-phenylene)-alt-2,5-thiophene](P3)are designed,synthesized and complexed with SWCNTs as thermoelectric composites.The electrical conductivities of the CPEs/SWCNTs(P2/SWCNTs,and P3/SWCNTs)nanocomposites are much higher than those of non-CPEs/SWCNTs(P1/SWCNTs)nanocomposites.Among them,the electrical conductivity of P2/SWCNTs with a ratio of 1:4 reaches 3686 S·cm^-1,which is 12.4 times that of P1/SWCNTs at the same SWCNT mass ratio.Moreover,CPEs/SWCNTs composites(P2/SWCNTs)display remarkably improved thermoelectric properties with the highest power factor(PF)of 163μW·m^-1·K^-1.In addition,a thermoelectric generator is fabricated with P2/SWCNTs composite films,and the output power and power density of this generator reach 1.37μW and 1.4 W·m;(cross-section)at△T=70 K.This result is over three times that of the thermoelectric generator composed of non-CPEs/SWCNTs composite films(P1/SWCNTs,0.37μW).The remarkably improved electrical conductivities and thermoelectric properties of the CPEs/SWCNTs composites(P2/SWCNTs)are attributed to the enhanced interaction.This method for constructing CPEs/SWCNTs composites can be applied to produce thermoelectric materials and devices.     

Thermal vibration in superionic conducting glass 5Agl–3Ag2O–2V2O5

The X-ray diffraction measurement for superionic conducting glass 5Agl–3Ag₂O–2V₂O₅ was carried out at 12, 100, 200 and 290 K. The temperature dependence of structure factor S(Q) of 5Agl–3Ag₂O–2V₂O₅ has been discussed based on the theoretical treatment that includes thermal vibration of atoms in noncrystalline materials. The effective overall Debye–Waller temperature parameter B increases with the increase of temperature.     

Synthesis and thermoelectric properties of Bi-doped SnSe thin films

Bi doped n-type SnSe thin films were prepared by chemical vapor deposition (CVD) and their structure and thermoelectric properties were studied. The x-ray diffraction patterns, x-ray photoelectron spectroscopy, and microscopic images show that the prepared SnSe thin films were composed of pure SnSe crystals. The Seebeck coefficients of the Bi-doped SnSe were greatly improved compared to that of undoped SnSe thin films. Specifically, Sn_0.99Bi_0.01Se thin film exhibited a Seebeck coefficient of -905.8μV·K^-1 at 600 K, much higher than 285.5 μV·K^-1 of undoped SnSe thin film. Further first-principles calculations reveal that the enhancement of the thermoelectric properties can be explained mainly by the Fermi level lifting and the carrier pockets increasing near the Fermi level due to Bi doping in the SnSe samples. Our results suggest the potentials of the Bi-doped SnSe thin films in thermoelectric applications.     

Synthesis of ternary compound in H-S-Se system at high pressures

The chemical reaction products of elemental sulfur (S), selenium (Se), and molecular hydrogen (H₂) at high pressures and room temperature are probed by Raman spectroscopy. Two known compounds H₂S and H₂Se can be synthesized after laser heating at pressures lower than 1 GPa. Under further compression at room temperature, an H₂S-H₂Se and an H₂S-H₂Se-H₂ van der Waals compounds are synthesized at 4 GPa and 6 GPa, respectively. The later is of guest-host structure and can be identified as (H₂S)_x(H₂Se)_(2-x)H₂. It can be maintained up to 37 GPa at least, and the stability of its H₂Se molecules is extended:the H-Se stretching mode can be detected at least to 36 GPa but disappears at 22 GPa in (H₂Se)₂H₂. The pressure dependence of S-H and Se-H stretching modes of this ternary compound is in line with that of (H₂S)₂H₂ and (H₂Se)₂H₂, respectively. However, its hydrogen subsystem only shows the relevance to (H₂S)₂H₂, indicating that this ternary compound can be viewed as H₂Se-replaced partial H₂S of (H₂S)₂H₂.     

Investigation of reduced graphene oxide effects on ultra-violet detection of ZnO thin film

The reduced graphene oxide (rGO) incorporated ZnO thin films were fabricated by dip-coating method. The Raman and FT-IR spectra of 0.075 wt% incorporated composite film showed reduction of GO in composite film. The transmittanceProd. Type: FTP spectra have shown that rGO incorporation increase the visible light absorption of ZnO thin film while the calculated band gaps of samples were decreased from 3.28 to 3.25 eV by increasing the rGO content. The linear trend of I–V curve suggests an ohmic contact between ZnO and rGO. Besides, it was found that by increasing the rGO content, the electrical resistivity was decreased from 4.32×10² Ω cm for pure ZnO film to 2.4×10¹ Ω cm for 0.225 wt% rGO incorporated composite film. The composite photodetectors not only possessed a desirable UV photosensitivity, but also the response time of optimum sample containing 0.075 wt% rGO was reduced to about one-half of pure ZnO thin film. Also, the calculated signal to noise (SNR) showed that highly conductive rGO in composite thin films facilitate the carrier transportation by removing the trapping centers. The mechanism of photoresponsivity improvement of composite thin films was proposed by carrier transportation process.     

Realization of semiconducting Cu2Se by direct selenization of Cu(111)

Bulk group IB transition-metal chalcogenides have been widely explored due to their applications in thermoelectrics. However, a layered two-dimensional form of these materials has been rarely reported. Here, we realize semiconducting Cu₂Se by direct selenization of Cu(111). Scanning tunneling microcopy measurements combined with first-principles calculations allow us to determine the structural and electronic properties of the obtained structure. X-ray photoelectron spectroscopy data reveal chemical composition of the sample, which is Cu₂Se. The observed moiré pattern indicates a lattice mismatch between Cu₂Se and the underlying Cu(111)-$\sqrt{3}$×$\sqrt{3}$ surface. Differential conductivity obtained by scanning tunneling spectroscopy demonstrates that the synthesized Cu₂Se exhibits a band gap of 0.78 eV. Furthermore, the calculated density of states and band structure demonstrate that the isolated Cu₂Se is a semiconductor with an indirect band gap of ～ 0.8 eV, which agrees quite well with the experimental results. Our study provides a simple pathway varying toward the synthesis of novel layered 2D transition chalcogenides materials.     

Facile fabrication of highly flexible,porous PEDOT: PSS/SWCNTs films for thermoelectric applications

High-performance organic composite thermoelectric(TE)materials are considered as a promising alternative for harvesting heat energy.Herein,composite films of poly(3,4-ethyienedioxythiophene):poly(styrene sulfonate)/single-walled carbon nanotubes(PEDOT:PSS/SWCNTs)were fabricated by utilizing a convenient solution mixing method.Thereafter,the as-prepared hybrid films were treated using sulfuric acid(H₂SO₄)to further optimize the TE performance.Film morphological studies revealed that the sulfuric acid treated PEDOT:PSS/SWCNTs composite samples all possessed porous structures.Due to the successful fabrication of highly conductive networks,the porous nano-architecture also exhibited much more excellent TE properties when compared with the dense structure of the pristine samples.For the post-treated sample,a high power factor of 156.43μW·m^-1·K^-2can be achieved by adjusting the content of CNTs,which is approximately 3 orders of magnitude higher than that of the corresponding untreated samples(0.23μW·m^-1·K^-2).Besides,the obtained films also showed excellent mechanical flexibility,owing to the porous nanostructure and the strong p–p interactions between the two components.This work indicates that the H₂SO₄ treatment could be a promising strategy for fabricating highly-flexible and porous PEDOT:PSS/SWCNTs films with high TE performances.     

Magneto-optical properties and exciton dynamics in diluted magnetic semiconductor nanostructures

Nanostructures of diluted magnetic semiconductors were fabricated to study novel magneto-optical properties that are derived from quantum confined band electrons interacting with magnetic ions. Quantum dots (QDs) of Cd_0.97Mn_0.03Se were grown by the self-organization on a ZnSe substrate layer. QDs of Zn_0.69Cd_0.23Mn_0.08Se and quantum wires (QWRs) of Cd_0.92Mn_0.08Se and Zn_0.69Cd_0.23Mn_0.08Se were fabricated by the electron beam lithography. A single quantum well (QW) of ZnTe/Zn_0.97Mn_0.03Te and double QWs of Cd_0.95Mn_0.05Te–CdTe were grown by molecular beam epitaxy. Magneto-optical properties and the formation and relaxation dynamics of excitons were investigated by ultrafast time-resolved photoluminescence (PL) spectroscopy. Excitons in these nanostructures were affected by the low-dimensional confinement effects and the interaction with magnetic ion spins. The exciton luminescence of the Cd_0.97Mn_0.03Se QDs shows the confined exciton energy due to the dot size of 4–6 nm and also shows marked increase of the exciton lifetime with increasing the magnetic field. The QDs of Zn_0.69Cd_0.23Mn_0.08Se fabricated by the electron beam lithography display narrow exciton PL spectrum due to the uniform shape of the dots. The exciton luminescence from the QWRs of Cd_0.92Mn_0.08Se and Zn_0.69Cd_0.23Mn_0.08Se shows the influence of the one-dimensional confinement effect for the exciton energy and the luminescence is linearly polarized parallel to the wire direction. The transient PL from the ZnTe/Zn_0.97Mn_0.03Te QWs displays, by the magnetic field, the level crossing of the exciton spin states of the nonmagnetic and magnetic layers and the spatial spin separation for the excitons. Cd_0.95Mn_0.05Te–CdTe double QWs show the injection of the spin polarized excitons from the magnetic well to the nonmagnetic QW.     

Thermodynamic properties of the clathrate-type silver-oxide Ag6O8AgHF2

We report normal-state and superconducting properties of the clathrate-type silver-oxide Ag₆O₈AgHF₂. We present electrical resistivity, DC- and AC-susceptibility and specific-heat measurements of single crystalline Ag₆O₈AgHF₂. In the normal state, Ag₆O₈AgHF₂ exhibits metallic conductivity and a phase transition near 110 K, possibly a structural phase transition as observed in the related compound Ag₆O₈AgNO₃. The onset of superconductivity of our samples is observed around 1.2–1.5 K, and the H–T phase diagram is determined for the first time. The upper critical field H_c2(0) is estimated to be about 2000–2200 Oe and the coherence length ξ_GL(0) to be 40 nm.     

Porous WO<Subscript>3</Subscript>/reduced graphene oxide composite film with enhanced electrochromic properties

The porous WO₃/reduced graphene oxide (rGO) composite films are prepared on indium–tin oxide (ITO) glass by sol-gel method. The mixture sol combines peroxotungstic acid solution with rGO dispersion reduced by ethylene glycol (EG). The excessive EG and other organic additives are subsequently removed by annealing, which leads to the formation of porous structure. Compared with pure WO₃ film, WO₃/rGO composite film shows improved electrochromic performance because of enhanced double insertion/extraction of ions and electrons. It realizes a large optical modulation (64.2 % at 633 nm), fast switching speed (9.5 s for coloration and 4.5 s for bleaching), good cycling stability as well as reversibility.     

基于中性水凝胶/取向碳纳米管阵列高电压柔性固态超级电容器

随着科技发展和时代进步,发展质轻便携、安全环保的高性能储能器件变得日趋重要,对柔性固态超级电容器的研究也应运而生.柔性电极材料及电解质的选用是设计柔性固态超级电容器的关键因素,近年来一直是研究的热点.考虑到环境污染及实际需求问题,本文采用中性凝胶电解质对具有高比表面积、良好导电性及取向性的碳纳米管阵列进行包埋处理,所形成的柔性复合薄膜作为电极材料,设计制备三明治结构的柔性超级电容器件.通过改变凝胶电解质中所加入的无机盐电解质种类,调控器件的电化学储能性质.最终在聚乙烯醇PVA-NaCl作为凝胶电解质时,整个器件比容量最高达104.5 mF·cm~(–3),远高于有机离子凝胶与碳管阵列形成的复合器件以及无规分布的碳纳米管与水凝胶形成的复合器件,同时获得了0.034 mW·h·cm~(–3)的最大能量密度,并且具有良好的倍率性能、循环稳定性及抑制自放电的效果,并在高电压1.6 V下依然保持良好的化学稳定性.这种中性凝胶/碳管阵列复合超级电容器件不仅满足了绿色安全、柔性便携的要求,未来在医学可植入器件等领域也具有很好的应用前景.     

Synthesis and ionic conductivity of new layered perovskite compound, Ag2La2Ti3O10

A new layered perovskite compound, Ag₂La₂Ti₃O₁₀, was synthesized by an ion-exchange reaction of M₂La₂Ti₃O₁₀ (M = Na,K) with a AgNO₃ molten salt. The crystal structure and the ionic conductivity of the ion-exchanged compound were investigated. The ionic conductivities attributed to the interlayer silver ions were observed at high temperatures. The ionic conductivity of Ag₂La₂Ti₃O₁₀ was much higher than that of Na₂La₂Ti₃O₁₀, while the interlayer sodium ions in Na₂La₂Ti₃O₁₀ and silver ions in Ag₂La₂Ti₃O₁₀ have almost the same rock-salt type coordination. The higher conductivity of Ag₂La₂Ti₃O₁₀ is probably due to the higher polarizability of silver ions.     

Novel closed-cycle reaction mode for totally green production of Cu1.8Se nanoparticles based on laser-generated Se colloidal solution

Non-stoichiometric copper selenide (Cu_2-xSe, x=0.18～0.25) nanomaterials have attracted extensive attentions due to their excellent thermoelectric, optoelectronic and photocatalytic performances. However, efficient production of Cu_2-xSe nanoparticles (NPs) through a green and convenient way is still hindered by the inevitable non-environmentally friendly operations in common chemical synthesis. Herein, we initially reveal the coexistence of seleninic acid content and elemental selenium (Se) NPs in pulsed laser-generated Se colloidal solution. Consequently, we put forward firstly a closed-cycle reaction mode for totally green production of Cu_1.8Se NPs to exclude traditional requirements of high temperature and toxic precursors by using Se colloidal solution. In such closed-cycle reaction, seleninic acid works as the initiator to oxidize copper sheet to release cuprous ions which can catalyze the disproportion of Se NPs to form SeO₃^2- and Se^2- ions and further produce Cu_2-xSe NPs, and the by-product SeO₃^2- ions promote subsequent formation of cuprous from the excessive Cu sheet. In experiments, the adequate copper (Cu) sheet was simply dipped into such Se colloidal solution at 70 ℃, and then the stream of Cu_1.8Se NPs could be produced until the exhaustion of selenium source. The conversion rate of Se element reaches to more than 75% when the size of Se NPs in weakly acidic colloidal solution is limited between 1 nm and 50 nm. The laser irradiation duration shows negative correlation with the size of Se NPs and unobvious impact to the pH of the solution which both are essential to the high yield of Cu_1.8Se NPs. Before Cu sheet is exhausted, Se colloidal solution can be successively added without influences to the product quality and the Se conversion rate. Such green methodology positively showcases a brand-new and potential strategy for mass production of Cu_2-xSe nanomaterials.     

含硫宽禁带Ga2Te3基热电半导体的声电输运特性

目前对宽禁带半导体热电材料的研究开始升温, 原因是本征情况下宽禁带半导体往往具有低的热导率和高的Seebeck系数. Ga₂Te₃ 是一类带有缺陷的宽禁带半导体, 其在临界温度680± 10 K和757± 10 K处会参与共析转变和包晶反应, 因此会产生反应热. 本次工作采用少量的S元素等电子替换Ga₂Te₃中的Te元素, 观察到在临界温度附近热焓的变化, 但没有相变发生. 受热焓变化的影响这类材料在临界温度附近出现了较活跃的声电输运行为, 具体表现为热容和Seebeck系数(α)明显增大及热扩散系数(热导率)和电导率下降. 例, 对于x=0.05的材料, 其α值从596 K 时的376.3(μV·K^-1)迅速增大到695 K时的608.2(μV·K^-1), 然后又随温度升高到764 K时迅速降低到213.8(μV·K^-1). 在596 K到812 K范围, Seebeck系数和电导率几乎随温度均呈Z字形变化. 这些输运行为的变化揭示了在Ga₂Te₃基半导体中声子和载流子的临界散射特点, 这种临界散射特征对以后的继续研究具有重要的参考价值.