Sb2S3太阳能电池的研究进展

硫化锑(Sb2S3)是一种性质稳定的V-Ⅵ族直接带隙半导体材料,地壳中含量丰富、安全无毒.由于Sb2S3具有较高的光吸收系数(α≈105 cm-1),并且带隙宽度适中、易于调控(1.5 ～2.2 eV),覆盖了大部分可见光光谱,因此被视为最有希望得到应用的太阳能电池材料之一.本文结合近年来Sb2S3的相关研究工作,对Sb2S3太阳能电池的研究进展和发展现状进行了阐述,并展望了其发展趋势.     

n(Sm3+)/n(S2O2-3)对液相自组装法制备Sm2S3薄膜的影响

采用液相自组装法,以氯化钐( SmCl3·6H2O)和硫代硫酸钠(Na2S2O3·5H2O)为原料,在不同n(Sm3 )/n(S2O2-3)(物质的量比)条件下,于硅基板上制备了α-Sm2S3光学薄膜.利用X射线衍射仪(XRD)、光电子能谱分析(XPS)、原子力显微镜(AFM)和紫外-可见吸收光谱仪(UV-Vis)对SmS3薄膜的物相组成、表面形貌和光学性能进行了表征.结果表明:所制备的Sm2S3薄膜为α-Sm2S3,在一定范围内,随着n(Sm3+)/n(S2O2-3)的增加,α-Sm2S3薄膜的结晶性先增强后降低,并表现出(105)晶面取向生长的特征.紫外透射光谱分析表明,当n(Sm3+)/n(S2O2-3)=1∶2时,Sm2S3薄膜在可见光范围内透过率高达85;,禁带宽度为4.12 eV.     

Ca2+掺杂γ-La2S3多晶的制备

本文以气固反应硫化得到的γ-La2S3粉体为原料,采用热压烧结的方法制备出了γ-La2S3多晶体片.研究了不同Ca2+掺杂量对得到粉体相结构的影响,并分析了烧结温度、保温时间对多晶体γ-La2S3红外透过率的影响.结果表明:掺入碱土金属离子Ca2+有利于低温获得稳定的高温型γ-La2S3相,在Ca/La物质的量比为1:5～1:15时能得到纯相的γ-La2S3粉体.在烧结温度为1100 ℃,保温时间为1 h时制备出的γ-La2S3多晶体片,晶粒细小均匀,无明显气孔,在10～14 μm波段的最大红外透过率约为40;.     

γ-Ce2S3大红色料表面附着ZnO及对H2S释放的影响

以市售大红色料γ-Ce2S3为原料,六水合硝酸锌(Zn(NO3)2·6H2O)为锌源,无水碳酸钠(Na2CO3)为沉淀剂,醇水混合溶液为反应介质,采用非均相沉淀法在γ-Ce2S3色料表面附着一层ZnO,研究含Zn前驱体在色料颗粒表面附着形态及附着ZnO后对色料受热后H2S释放的影响.研究结果表明:以乙醇与水混合溶液为反应介质,沉淀离子采用同步滴加方式,滴加速度0.3 mI/min,Zn与γ-Ce2S3的摩尔比为0.2时,300 ℃热处理30 min能够在γ-Ce2S3颗粒表面均匀附着一层ZnO,且色料仍保持鲜艳的红色,其色度L*、a*和b*值分别为34.17、33.10和22.80;表面附着ZnO后对H2S的释放有明显的抑制作用,色料在350℃保温10 min,H2S释放浓度由未附着ZnO的4.21 mg/m3降至0.     

电沉积法制备Bi2S3薄膜研究

采用阴极恒电压法在ITO导电玻璃表面沉积了Bi2S3薄膜,利用X射线衍射(XRD)、原子力显微镜(AFM)对制备的薄膜进行了表征.研究了pH值、沉积时间、沉积液浓度等工艺因素对薄膜的影响.结果表明:电沉积制备Bi2S3薄膜的过程中,合适的Bi3+与S2O32-的浓度水平是至关重要的;在电沉积溶液pH=6.5,沉积时间为20 min,沉积电压为1 V,加入柠檬酸三钠作络合剂的情况下,得到沿(240)晶面生长良好的Bi2S3薄膜,薄膜组成均匀致密;增加沉积溶液pH值,薄膜的结晶程度逐渐提高,红外透过比提高.     

A quasi-layer structure of trinuclear molybdenum(IV) cluster, [Mo3S7(S2CNEt2)3]I·S8

The title compound, [Mo₃(₃-S)(-S₂)₃(S₂CNEt₂)₃]I·S₈, was obtained by solid state reaction of (NH₄)₂MoS₄, Et₂NCS₂Na, and Et₄NI at low heating temperature and crystallizes in space group P with a = 13.572(3), b = 13.813(4), c = 13.239(3) Å, = 92.63(3), = 100.15(3), = 117.89(2)°, V = 2136(2) ų, and D _calc. = 2.08 g/cm³ for Z = 2. The structure reveals that it consists of a trinuclear Mo cluster molecule, [Mo₃S₇(S₂CNEt₂)₃]I, and one S₈, which are connected to form a quasi-layer structure by the interaction between S₈ and the S atoms of the cluster molecule.     

Raman spectroscopy studies of xNa2S+(1−x)B2S3 glasses and polycrystals

The Raman spectra of binary xNa₂S+(1−x)B₂S₃ glasses and polycrystals have been measured for the first time and are used to develop a structural model of the sodium thioborate glasses. The Raman spectra confirm our previous infrared (IR) experimental conclusions that the structure of vitreous (ν-B₂S₃) is comprised of B3(0) groups and six-membered rings. It was also found that as sodium sulfide is added to the glass in the low alkali (x<0.35) glass forming region, the B4 groups are formed at the expense of the B3(0) groups first and then from the six-membered ring groups. The Raman spectra are also consistent with the presence of a pyramidal structural arrangement of B4 groups with trigonally coordinated sulfur atoms. This structure could explain the existence of the super-stoichiometric amounts of B4 groups found using nuclear magnetic resonance (NMR). Glasses in the high alkali region (0.50<x<0.80) progressively change from being comprised of metathioborate rings to being comprised of B3(3) groups. The Raman spectra also confirms the IR spectra which saw no evidence of B3(2) groups in these sodium thioborate glasses.     

Cyclic dithiophosphate salts [Et3NH+[(OCH2CMe2CH2O)P(S)S]− and [Et3NH]+[CH2{6-t-Bu-4-Me-C6H4O}2P(S)S]−

X-ray structures of the cyclic dithiophosphate salts [Et₃NH]⁺[(OCH₂CMe₂CH₂O)P(S)(S)]^– (1) and [Et₃NH]⁺[CH₂{6-t-Bu-4-Me-C₆H₄O}₂P(S)S]^– (2) have been determined. Crystal data for 1: Tetragonal, P4₂/m, a = 13.416(7), b = 13.416(2), c = 9.153(2) Å, and Z = 4. Crystal data for 2 = Monoclinic, P2₁/c, a = 19.1112(17), b = 14.649(9), c = 22.7166(19) Å, = 102.883(7)°, and Z = 8. The six- and eight-membered rings in 1 and 2 have chair and boat-chair conformations respectively. Both of these compounds show weak N—H······S hydrogen bonds; interestingly, in 2 both two-center and three-center hydrogen bonds are observed in the solid state.     

Silver metal enhanced photoluminescence of Tm3+ doped GeS2–Ga2S3–CsCl glasses

We report silver metal enhanced near-IR and infrared-to-visible upconversion luminescence in Tm³⁺ doped 70GeS₂–10Ga₂S₃–20CsCl (in mol. %) glasses. The metal embedded glasses are prepared under controlled crystallization. Upon 808 nm excitation three fold enhancement of emissions is observed in the visible (446 nm, 496 nm, and 532 nm) and near infrared (1230 nm, 1450 nm and 1480 nm) regions. The possible mechanism responsible for the enhanced luminescence is discussed.     

Ion conductive chalcohalide glasses in LiI–Ga2S3–GeS2 system

The electric properties of LiI containing chalcohalide glasses in the system Ga₂S₃–GeS₂ were studied by means of impedance spectroscopy and potentiostatic chronoamperometry. Two sets of the samples were prepared by direct synthesis from elements and compounds in evacuated quartz ampoules. The prepared glasses were as follows: xLiI–xGa₂S₃–(100?2x)GeS₂, x = 15, 20, 25 and 20LiI–xGa₂S₃–(80?x)GeS₂, x = 0, 5, 10, 15 and 20. In the first set the concentration of LiI increased and the second set was prepared to study the influence of Ga₂S₃ on the properties of the glasses. Additional aim of this work was to compare the electric properties of LiI containing Ga₂S₃–GeS₂ glasses with analogous AgI containing Ga₂S₃–GeS₂ glasses recently studied by us. The conductivity of the LiI containing glasses in the Ga₂S₃–GeS₂ system was higher and the activation energy was lower than in the analogous AgI containing system. The residual electronic (hole) conductivity remained similar in both systems being almost negligibly low. Raman spectroscopy proved the influence of LiI as well as Ga₂S₃ on glass structure, however interpretation of Raman spectra of these glasses is complicated due to small mass difference between gallium and germanium.     

New chalcohalide glasses from the GeS2–In2S3–CsCl system

New chalcohalide glasses from GeS₂–In₂S₃–CsCl pseudo-ternary system were prepared using the conventional melt-quenching method and its glass-forming region has been determined. The differences ΔT (T_P ? T_g) of partial glasses are large enough (>100 K) to permit the preparation of performs of considerable size. With the increased content of CsCl, the visible absorption edge (λ_vis) of these glasses indicates a distinct blue shift while a clear drop of their glass transition temperatures can be seen. The ultrafast non-linearity of partial glasses was measured using the Kerr shutter technique. The non-linear refractive index, n₂, was estimated to be in the magnitude of 10^?14 cm²/W. Widely transparent range, good glass-forming ability, higher χ⁽³⁾ and large electronic ultrafast OKE response make these glasses the potential applications in current photonic fields.     

Piranha化学法与化学浴沉积制备Sb2S3薄膜

采用Piranha化学法与化学浴沉积技术相结合,在玻璃基板上成功制备了Sb2S3薄膜.研究了Piranha溶液不同处理时间对基板表面润湿性的影响,同时研究了Sb2S3薄膜相组成及形貌.结果表明,Piranha溶液能够有效地改善玻璃基板表面的润湿性,当处理时间为25 min时,基板表面润湿角达到最低值12.83°.Piranha溶液处理后的基板对于Sb2S3薄膜的沉积具有积极的诱导作用.沉积得到薄膜经200℃煅烧1h,由非晶态转变为正交相,薄膜在基板表面以单层球形颗粒平铺堆积生长.     

Synthesis and characterization of the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph4P)2[{Mo2Cu2O2S2(S2)2}3(μ6-S)]

The complex (Ph₄P)₂[Mo₂S₂O₂(S₂)(S₄)] reacts with CuBr to give the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph₄P)₂[{Mo₂Cu₂O₂S₂(S₂)₂}₃(₆-S)] (1), which crystallizes in the triclinic space group P1¯, a = 14.445(5), b = 15.396(5), c = 18.858(5) Å, = 103.12(3), = 101.93(2), = 113.92(3)°, and V = 3517(2) ų for Z = 2. The anion 1 can be described as a cage with S^2– at the center binding to six Cu atoms; the cage has two big windows each composed of a puckered Cu₃S₆ 9-membered ring.     

Compositional trends in low-temperature photoluminescence of heavily Er-doped GeS2–Ga2S3 glasses

The influence of temperature and glass composition on the photoluminescence (PL) efficiency of Er³⁺ ions embedded in (GeS₂)_100?x(Ga₂S₃)_x (x = 20, 25 and 33 mol%) glasses has been studied. The typical 4f–4f emission bands of Er³⁺ ions at around 830, 1000 and 1550 nm have been observed in the whole investigated temperature range from 300 K down to 10 K for all the compositions. New 4f–4f luminescence bands, in excess of the three basic ones, have been observed at 670, 870, 1120, 1260 and 1350 nm for (GeS₂)₇₅(Ga₂S₃)₂₅ glass composition, and are tentatively assigned to ²H_9/2 → ⁴I_11/2, ⁴G_11/2 → ⁴F_9/2, ²H_11/2 → ⁴I_11/2, ⁴F_7/2 → ⁴I_9/2 and ⁴F_3/2 → ⁴I_9/2 transitions, respectively. Thus a considerable influence of GeGaS host composition on the efficiency of 4f–4f transitions of embedded Er³⁺ ions is documented with the outcome that (GeS₂)₇₅Ga₂S₃)₂₅ composition appears near optimal for the emission efficiency of Er³⁺ ions. With decreasing temperature the PL efficiency is enhanced considerably with pronounced narrowing of all bands. In the case of the strongest PL band at ~ 1550 nm, corresponding to ⁴I_13/2 → ⁴I_15/2 transition, the narrowing at low temperature is further accompanied by the resolution of well pronounced fine structure due to “crystal field” splitting of corresponding electronic terms. The relationship between the photoluminescence and reflectance spectra as a function of Er content has been discussed.     

水解法制备SiO2包裹γ-Ce2S3色料及其耐酸性研究

本文以市售大红色料γ-Ce2S3为原料,正硅酸乙酯(TEOS)为硅源,采用水解法制备了SiO2包裹γ-Ce2S3色料,采用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电镜(FE-SEM)、能谱仪(EDS)、傅立叶红外光谱(FT-IR)等技术对色料进行了表征.研究结果表明,在TEOS/H2O质量比为1∶20、Ce/Si摩尔比为3∶1、水解温度为45℃、水解用纯水滴加速率为0.3 mL/min的条件下,可获得均匀致密的无定型二氧化硅(SiO2·xH2O)包裹层,其厚度为100 nm左右,包裹色料仍保持鲜艳的红色,其色度L*、a*和b*值分别为26.82、35.53和29.60;该条件下所得包裹色料的耐酸性最佳,未包裹色料浸泡于1 mol/L的盐酸中半分钟之内已失去红色,而该色料浸泡2h其呈色仍没有明显变化.     

衬底温度对In2S3薄膜结构及其性能的影响

采用超声喷雾热解法,在玻璃基底上一步合成了In2S3薄膜.研究了衬底温度对In2S3薄膜的结构、表面形貌、电学和光学性能影响.结果表明:所制备的In2S3薄膜均具有沿(220)面择优取向生长特性且无其他杂相,衬底温度对薄膜的均匀性、致密度、结晶程度均有明显影响,并因此影响薄膜的光电性能.薄膜的导电件随着衬底温度的升高迅速增强,但足在衬底温度为350℃时有所降低.衬底温度为300℃所制备的薄膜在可见光区透光率最高达到90;以上,禁带宽度达到2.43 eV.     

不同有机物模板作用下Bi2S3的制备与表征

以硝酸铋为铋源、硫脲为硫源,分别以小分子有机物-巯基乙酸、柠檬酸及聚合物半导体-羧基化PPV(羧基化的聚对苯乙炔)为模板,利用水热反应法制备了不同形貌的Bi2S3微晶,并对产物用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见-近红外光谱(UV-Vis-Near-IR)等进行表征.结果表明,所制备的Bi2S3微晶为斜方晶系的辉铋矿;在巯基乙酸的作用下,Bi2S3排列成直径约为2～3 μm的花状微晶;在柠檬酸的作用下,Bi2S3晶体呈絮状,结成直径约为2μm左右的绒球;在羧基化PPV的作用下,Bi2S3构成直径约为2μm的绒球.通过由UV-Vis-Near-IR光谱绘制的(αhv)2～hv曲线图计算得到,在不同有机物模板作用下得到的Bi2S3微晶的能带间隙均大于无模板作用得到的Bi2S3,且羧基化PPV的作用效果优于小分子有机物,使能带间隙提高为1.64 eV.     

微波合成Bi2S3/g-C3N4复合光催化剂及其光催化性能研究

采用微波合成法制备了Bi2 S3/g-C3 N4复合光催化剂,利用X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、紫外可见-漫反射吸收光谱(Uv-vis)、物理吸附仪(BET)等对其进行了表征,以罗丹明B(RhB)为目标化合物对其光催化性能进行了评价.结果表明,与纯Bi2 S3和g-C3 N4相比,复合样品的禁带宽度变小,比表面积增大,光生载流子的复合效率降低,显著提高了其光催化降解RhB的效率.复合样品5-CNBS对RhB的降解率达99;以上,分别是纯g-C3 N4和Bi2 S3单体对RhB降解效率的1.59倍和4.95倍.     

Microstructure and thermal properties of the GeS2–In2S3–CsI glassy system

A new series of chalcohalide glasses in the GeS₂–In₂S₃–CsI pseudo-ternary system were prepared by conventional melt-quenching method. The glass-forming region was determined and it is mainly situated in the GeS₂-rich domain. The glasses have relatively high glass transition temperatures (T_g ranges from 335 to 405 °C) and good thermal stabilities. Based on the Raman spectra, it can be speculated that the glassy net is mainly constituted by [GeS₄] and [InS_4?xI_x] tetrahedra, which are interconnected by the bridging sulfur atoms. And the ethane-liked structural units [S₃Ge–GeS₃] can be formed because of the lacking of sulfur. Cs⁺ ion, which was added from CsI, exists as the nearest neighbor of I^? ion.     

Synthesis and crystal structure of 3-ammoniumphenyl sulfone selenate, 3-aminophenyl sulfone [C12H14N2O2S]SeO4 · [C12H12N2O2S]

The crystal structure of [C₁₂H₁₄N₂O₂S]SeO₄ · [C₁₂H₁₂N₂O₂S] was determined by X-ray diffraction on single crystal. Crystals are orthorhombic, space group Pbca, with cell parameters a = 11.545 (1), b = 8.143 (1), c = 55.783(1)Å, V = 5244.2 (8)ų and Z = 8. The structure can be described as organic layers built by [C₁₂H₁₄N₂O₂S]²⁺ cations and [C₁₂H₁₂N₂O₂S] molecules, parallel to ab plane, between which the inorganic groups SeO ₄ ^2? are inserted. In this atomic arrangement, H-bonds between the different species play an important role in the three-dimensional network cohesion.