两步法制备CIGS薄膜的工艺研究

本文主要研究了"预制层硒化法"制备铜铟镓硒(CIGS)薄膜的工艺。采用磁控溅射的方式制备In、Cu-Ga金属预制层,然后进行硒化(450℃)以及退火处理(550℃)。SEM结果表明,在室温下溅射沉积In薄膜,并且采用Mo/Cu-Ga/In/Cu-Ga/In的叠层顺序,可以获得平整致密的CIGS薄膜。XRD和SEM测量显示,以单质硒作为硒源,在450℃的硒化之后生成分离的CIS和CGS相,惰性氛围的高温退火可以使分离的CIS和CGS相互融合,形成均一化的CIGS四元化合物。在此基础上,最终完成的CIGS电池光电转换效率为7.5%。     

TiCl4水解法制备的阻挡层对染料敏化太阳能电池光电性能的影响

通过不同浓度的TiCl₄溶液水解, 在光阳极导电玻璃(FTO)基底上制备了阻挡层薄膜, 以此来抑制FTO表面的光生电子与I₃^-之间的复合反应, 采用X射线光电子能谱(XPS)和X射线衍射分别测试了阻挡层薄膜的组成, 用场发射扫描电子显微镜(FE-SEM)和紫外-可见(UV-Vis)分光光度计测试了阻挡层的形貌和对光的透过率, 在AM1.5和暗环境下分别测试了染料敏化太阳能电池(DSSC)的光电性能. 实验结果表明: 用此方法可以获得由TiO₂粒子组成的阻挡层薄膜; 阻挡层薄膜的形貌随着TiCl₄溶液浓度的增加而改变, 它的厚度随着TiCl₄溶液浓度的增加而增加; 引入阻挡层后, FTO对光的透过率都会下降; 这一薄膜的引入可以提高电池的光电性能, 用0.04 mol·L^-1的TiCl₄溶液制备的阻挡层对暗电流的抑制作用最为明显, 电池在AM1.5的条件下测试, 转换效率最高达7.84%.     

n型Bi2Te3-ySey温差电材料薄膜的电化学制备及表征

采用电化学控电位的方法在不锈钢基片上电沉积制备了Bi₂Te_3-ySe_y温差电材料薄膜。研究了电沉积溶液中硒含量与薄膜中硒含量的关系，考察了不同沉积电位对电沉积Bi₂Te_3-ySe_y薄膜的温差电性能的影响，并采用ESEM、EDS、XRD等方法对电沉积薄膜的形貌、成分及结构进行了分析。结果表明，在含有Bi³⁺、HTeO₂⁺和Se⁴⁺的电沉积溶液中，采用电化学沉积的方法，可实现铋、碲、硒三元共沉积，生成Bi₂Te_3-ySe_y半导体化合物。改变电沉积溶液组成，可控制Bi₂Te_3-ySe_y化合物中硒的掺杂浓度。-0.04 V沉积电位下制备的Bi₂Te_3-ySe_y薄膜较平整、致密，组成为Bi₂Te_2.7Se_0.3。退火处理可提高电沉积Bi₂Te_3-ySe_y薄膜的塞贝克系数，且控制沉积电位为-0.04 V下制备的Bi₂Te_3-ySe_y薄膜退火后的塞贝克系数为-123 μV·K^-1。     

高活性硫化铅电极的制备及在量子点敏化太阳能电池中的应用

为了提高量子点敏化纳晶薄膜太阳能电池的光电转换效率,我们通过连续在酸和多硫溶液中处理铅片制备了对多硫电解液具有高电催化活性的硫化铅电极. 通过电化学阻抗谱测试评价所制备硫化铅电极的催化活性,从而确定制备高效硫化铅电极的最佳条件. 以在最佳条件下制备的硫化铅为对电极、CdSe量子点敏化TiO₂纳晶薄膜为工作电极和多硫电解液组装成量子点敏化太阳能电池. 光电性能测试结果表明所制备的电极具有良好的催化活性和光电转换性能. 与已报导的方法相比,新方法大幅度地减少制备过程所需的时间,但却提高了所制备的硫化铅对电极的催化活性. 通过X射线衍射和扫描电镜测试表征了硫化铅的生成过程,探讨了催化活性提高的原因.     

染料敏化太阳能电池中大孔TiO2薄膜电极的制备及应用

采用溶胶-凝胶水热法制备了TiO₂纳晶薄膜电极，晶型为锐钛矿型。为了提高电极的光电性能，利用聚苯乙烯小球做造孔剂，制备了含有大孔隙的TiO₂纳晶薄膜电极，孔径约为200 nm，该电极具有较好的光漫反射性能，更重要的是球形大孔的存在，提高了凝胶电解质在TiO₂薄膜电极中的渗透和I₃^-离子的扩散性能，与不含大孔的TiO₂电极相比，电池的短路光电流提高约2 mA·cm^-2，光电转换效率提高0.6%。     

YAlO3的体色与缺陷平衡的关系

利用固相扩散法在1 450 ℃下制备了YAlO₃粉末样品和陶瓷片样品,并在不同温度和不同气氛(air, O₂ or N₂)下对样品进行退火处理调制了其缺陷浓度.基于漫反射光谱和交流阻抗谱分析了YAlO₃样品的体色与其缺陷浓度之间的关系.研究结果表明YAlO₃具有p型导电机理,其浅棕色体色是由阳离子空位引起的.在高温和氮气氛下处理该材料其缺陷浓度减少,体色变浅.第一性原理计算结果认为YAlO₃中的主要缺陷应该是铝空位V_Al^×.     

高结晶度方酸菁染料全溶液制备平面异质结有机太阳能电池

高结晶度有机半导体材料由于分子紧密堆叠,电荷迁移率高,但其在普通有机溶剂中溶解度低,溶液可加工性较差,限制了其在有机光电产品中的应用。本文设计合成了一种甲基修饰的高结晶度方酸菁类染料(DM-SQ),利用三氟乙酸溶剂溶液涂布制备DM-SQ薄膜。研究发现溶液制备的DM-SQ薄膜结晶度高,与真空沉积的DM-SQ薄膜比较,空穴迁移率更高(5.28×10_^-4 vs. 7.53×10_^-5 cm_² v_^-1 s_^-1)。以DM-SQ作为给体,PC₆₁BM作为受体,制备了平面异质结太阳能电池。溶液法制备的器件平均能量转换效率明显高于真空沉积器件(6.08±0.19％和3.56±0.22％)。     

含有TiO2刺球散射中心光阳极的设计及其在染料敏化太阳能电池的应用

采用水热法制备了一种刺球状TiO₂（NT）,将其作为光散射中心,与纳米晶TiO₂混合,制备成一种底层为P25薄膜（作为染料吸收层）,上层为添加NT散射层的混合结构的薄膜光阳极。探讨了NT添加量对薄膜性能的影响,实验结果表明,当NT与P25粉体的质量比为35%时电池光电性能最优,电池短路光电流密度为14.30 mA·cm^-2,其光电转换效率达到7.38%。质量比继续增大,当达到50%时电池性能有所下降,光电转换效率降为5.99%,同时染料吸附量也由73.2 μmol·cm^-2降到70.1 μmol·cm^-2。这表明过量的大颗粒TiO₂刺球散射中心会减少光阳极的比表面积从而降低染料的有效吸附量,并且还会引起不必要的反向散射,只有适量的散射中心才能得到最佳性能的太阳能电池器件。     

Gd2O3:Er3+上转换发光粉在染料敏化太阳电池中的应用

采用沉淀-煅烧法制备了Gd₂O₃:Er³⁺上转换发光粉,通过X射线衍射、扫描电子显微镜、能谱和荧光光谱对其进行了表征,并利用该发光粉具有上转换发光的特性将其应用于染料敏化太阳电池(DSSC)。结果表明,管状Gd₂O₃:Er³⁺上转换发光粉可增加电池对太阳光的吸收范围和吸收效率,提高电池的光电流和光电压。研究了掺杂量对电池性能的影响,当掺杂量为5wt%时,光电转换效率从5.93%升高到7.55%,提高约27%。     

TiO2纳米微球的制备及在染料敏化太阳能电池中的应用

以四氯化钛、盐酸为原料,制备出花状TiO₂纳米微球,利用扫描电子显微镜（SEM）、X射线衍射（XRD）等测试方法,对样品的结构和形貌进行了表征。为了提高TiO₂微球电池的光电性能,利用TiO₂微球作为反射层构造了双层结构的薄膜电极,结果表明,双层结构染料敏化太阳能电池在100 mW·cm^-2（1.5 G）光照条件下,短路光电流J_sc为17.64 mA·cm^-2,开路光电压Voc为0.74 V,填充因子FF为0.63和光电转化效率η为8.33%。相比TiO₂微球制备的太阳能电池,双层结构染料敏化太阳能电池光电转化效率提高至5.3倍。最后对电极中染料的吸附量、电极的光散射性能和电池的电化学阻抗做了进一步研究和分析,研究表明,双层结构电池增强光的捕获能力,从而提高光伏性能。     

Metal Precursor Influence on Performance of CuIn1-xGaxSe2 Films

CuIn_1-xGa_xSe₂ (CIGS) films were prepared by a two-stage method, in which Cu-In-Ga metallic precursors were firstly deposited on unheated Mo-coated soda lime glass substrates by direct current sputtering CuGa (20%Ga) and radio frequency sputtering In targets inan Ar atmosphere, followed by selenization at 520 oC for 40 min in Se vapor. By adjust-ing the sputtering thickness ratio of surface CuGa (20%Ga) and bottom CuGa (20%Ga) alloy layers in metal precursor, different CIGS thin films were fabricated. Through X-ray diffraction spectra, Raman spectra, local energy dispersive spectrometer, planar- and cross-sectional views of scanning electron microscopy measurements, it revealed that the CIGS thin films from selenization of metal precursor with CuGa:In:CuGa thickness ratio of 7:20:3 (sample-2-se) was of chalcopyrite structure with the preferred (112) orientation, and the grains sizes ranged from 0.5 μm to 2 μm, and sample-2-se had no binary compound phase of In-Se and order defect compound phase. Consequently, the results of illuminated current-voltage curve and quantum efficiency measurements showed that the CIGS film device made from sample-2-se had relative higher photo-electric conversion efficiency (3.59%) and good spectrum response.     

Structural,morphological, optical and sensing properties of SnSe and SnSe2 thin films as a gas sensing material

In this work, orthorhombic tin selenide thin films were grown onto three different substrates using an organophosphorus precursor (Ph₃PSe) via chemical vapor deposition. Structural, microstructural and morphological properties of the as-grown films were systematically investigated using XRD, ESEM and AFM respectively. Grain size, microstrain and dislocation were calculated and correlated with different factors. The effects of selenization temperature and substrate type on different film properties and gas sensing response of films deposited onto alumina substrates were investigated. XRD analysis reveals the appearance of a mixed phase as a function of temperature. Furthermore, substrate type plays a key role in the rate of appearance of each phase. EDAX analysis confirms the existence of the desired elements and detect the evaporation of selenium and the appearance of oxygen at higher temperatures. Atomic force microscopy (AFM) was used to investigate the surface topography of the grown thin films.Optical properties of the films grown onto glass and silicon substrates were studied. From the recorded optical data, a direct optical band gap in the range of 0.9–1.3 eV was obtained with an absorption coefficient α > 10⁴ cm⁻¹ throughout large spectral regions. Optical studies were remarkably affected by the obtained phase as well as the selenization temperature. Gas sensing properties of the samples deposited onto alumina substrates were examined as a new sensing material for detection of methane gas at different concentrations. SnSe sensors show high sensitivity, are reversible and exhibit fast response and recovery times compared to SnSe₂ sensors.     

8.01% CuInGaSe2 solar cells fabricated by air-stable low-cost inks

CuInGaSe(2) (CIGS), a promising thin film solar cell material, has gained lots of attention in decades due to its high energy conversion efficiency and potential lower manufacture cost over conventional Si solar cells. As a cheaper processing method compared to vacuum-based techniques, solution-based deposition has been successfully applied to fabricate electronic devices, such as transistors and solar cells. In this paper, we reported CIGS thin film solar cells with an energy conversion efficiency reaching up to 8.01% using air-stable, low-cost inks. The newly developed inks consist of commercially available, low-cost compounds and solvents and can be processed using a variety of printing and coating techniques. More importantly, the inks can produce CIGS films free of copper selenides and amorphous carbon, two common by-products from solution-based CIGS processes. The mechanism for the transformation from metal salt precursor films to CIGS absorber thin films and the influence of selenium vapour pressure on absorber film quality and photovoltaic device performance were investigated and discussed. High-quality CIGS films with micrometer-sized crystals were obtained by using higher selenization partial pressure.     

Highly efficient solution-processed CZTSSe solar cells based on a convenient sodium-incorporated post-treatment method

In CZTSSe solar cells,a simple sodium-incorporation post-treatment method toward solution-processed Cu_2Zn Sn S_4precursor films is presented in this work.An ultrathin Na Cl film is deposited on Cu_2Zn Sn S_4precursor films by spin-coating Na Cl solution.In subsequent selenization process,the introduction of Na Cl is found to be benefacial for the formation of Cu_(2-x)Se,which can further facilitate the element transportation,leading to dense and smooth CZTSSe films with large grains and less impurity Cu_2Sn(S,Se)_3phase.SIMS depth profiles confirm the gradient distribution of the sodium element in Na-doped absorbers.Photoluminescence spectra show that the introduction of appropriate sodium into the absorber can inhibit the band tail states.As high as 11.18%of power conversion efficiency(PCE)is achieved for the device treated with 5 mg m L~(-1)Na Cl solution,and an average efficiency of Na-doped devices is 10.71%,13%higher than that of the control groups(9.45%).Besides,the depletion width and the charge recombination lifetime can also have regular variation with sodium treatment.This work offers an easy modification method for high-quality Na-doped CZTSSe films and high-performance devices,in the meantime,it can also help to further understand the effects of sodium in CZTSSe solar cells.     

Single‐Step Sulfo‐Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors

Pentenary Cu₂ZnSn(S_ySe_1?y)₄ (kesterite) photovoltaic absorbers are synthesized by a one‐step annealing process from copper‐poor and zinc‐rich precursor metallic stacks prepared by direct‐current magnetron sputtering deposition. Depending on the chalcogen source—mixtures of sulfur and selenium powders, or selenium disulfide—as well as the annealing temperature and pressure, this simple methodology permits the tuning of the absorber composition from sulfur‐rich to selenium‐rich in one single annealing process. The impact of the thermal treatment variables on chalcogenide incorporation is investigated. The effect of the S/(S+Se) compositional ratio on the structural and morphological properties of the as‐grown films, and the optoelectronic parameters of solar cells fabricated using these absorber films is studied. Using this single‐step sulfo‐selenization method, pentenary kesterite‐based devices with conversion efficiencies up to 4.4 % are obtained.     

Inhibition of mycotoxin deoxynivalenol generation by using selenized glucose

Selenized glucose can be easily prepared via the selenization reaction of glucose using in situ generated NaHSe as the selenization reagent. The technique has been industrialized to produce the chemical in kilogram scale, making it an easily available material in laboratory presently. The selenized glucose may be widely used as the starting material for the preparation of selenium-containing catalysts, as the organoselenium additive for feeds, and as the efficient selenium-enriched foliar fertilizers. In this work, we found that treating Fusarium graminearum, a fungal pathogen inciting wheat scab disease, with selenium glucose could significantly inhibit the generation of the deoxynivalenol (DON) toxin, which might be a breakthrough for reducing the detriment of the wheat scab disease.     

Scrutinizing the facile growth of β-Ag2Se fine films

Silver selenide thin film is one of the best candidates for thermoelectric devices. In the previous report, we demonstrated that high-performanced [201] oriented β-Ag₂Se thin films can be prepared by direct metal surface element reaction (DMSER) solution selenization in a really short time at room temperature. However, the underlying mechanism of the fast reaction process were not discussed in depth. Herein, based on hard soft acid base (HASB) theory and strong oxidation, we further explored the possible reaction mechanism of the in-situ growth of β-Ag₂Se thin films as the function of the reaction time. The time-dependent experimental results showed that the formation of the β-Ag₂Se on elemental Ag precursor (∼690 nm thick) in Se/Na₂S precursor solution is in a growth driven mode with no obvious orientation or growth rate selections to the elemental Ag precursors. Our investigations provide a prerequisite for the further preparation of thermoelectric materials with excellent properties.     

Synthesis of High Quality CuInSe2 Films with Oxygen Precursor by Non-vacuum Process

The CuInSe₂ absorber was synthesized by non-vacuum process with a simple and low-cost method, which fabricated absorber layer of thin-film solar cell. The extra amount of Se was added into the ink to help reduction of the oxide and solid Se fountain was used to provide Se atmosphere during the selenization progress. The influence of same factors was investigated, such as the time of reduction in H₂, the time of selenization and the Se vapor pressure. The selenizaion, processed at 550 °C for 60 min with the Se vapor pressure at 1.90 kPa, resulted in high quality CuInSe₂ layer with very good chemical composition.     

Inhibition of mycotoxin deoxynivalenol generation by using selenized glucose

Selenized glucose can be easily prepared via the selenization reaction of glucose using in situ generated NaHSe as the selenization reagent. The technique has been industrialized to produce the chemical in kilogram scale, making it an easily available material in laboratory presently. The selenized glucose may be widely used as the starting material for the preparation of selenium-containing catalysts, as the organoselenium additive for feeds, and as the efficient selenium-enriched foliar fertilizers. In this work, we found that treating Fusarium graminearum, a fungal pathogen inciting wheat scab disease, with selenium glucose could significantly inhibit the generation of the deoxynivalenol (DON) toxin, which might be a breakthrough for reducing the detriment of the wheat scab disease.