Accelerated Sequential Deposition Reaction via Crystal Orientation Engineering for Low-Temperature,High-Efficiency Carbon-Electrode CsPbBr_(3) Solar Cells

Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation engineering strategy of PbBr_(2)precursor film to accelerate its reaction with CsBr precursor during two-step sequential deposition of CsPbBr_(3)films.Such a novel strategy is proceeded by adding CsBr species into PbBr_(2)precursor,which can tailor the preferred crystal orientation of PbBr_(2)film from[020]into[031],with CsBr additive staying in the film as CsPb_(2)Br_(5)phase.Theoretical calculations show that the reaction energy barrier of(031)planes of PbBr_(2)with CsBr is lower about 2.28 eV than that of(O2O)planes.Therefore,CsPbBr_(3)films with full coverage,high purity,high crystallinity,micro-sized grains can be obtained at a low temperature of 150℃.Carbon-electrode PSCs with these desired CsPbBr_(3)films yield the record-high efficiency of 10.27%coupled with excellent operation stability.Meanwhile,the 1 cm^(2)area one with the superior efficiency of 8.00%as well as the flexible one with the champion efficiency of 8.27%and excellent mechanical bending characteristics are also achieved.

CsPbBr_(3)晶体生长及变温霍尔效应研究

以定向凝固法提纯的CsPbBr_(3)多晶为原料,采用垂直布里奇曼法生长出尺寸为∅30 mm×70 mm的CsPbBr_(3)单晶。采用ICP-OES对提纯后的多晶测试表明,提纯后的CsPbBr_(3)多晶中杂质含量减少了28.7%。经XRD和EDS对切割得到的晶片分析发现,晶片的晶面方向属{210}晶面族,晶体中Cs、Pb、Br_(3)种元素分布均匀,原子百分含量符合化学计量比。采用傅里叶红外光谱仪和紫外-可见分光光度计对晶体的透过率测试显示,生长晶体在500~4000 cm^(-1)波数范围内的红外透过率超过75%,紫外短波截止边为552 nm,拟合计算出对应的禁带宽度为2.246 eV。选取7个不同温度点对CsPbBr_(3)单晶进行变温霍尔效应测试发现,生长晶体为P型导电,在250~300 K和300~350 K之间晶体中主要的载流子散射机制分别为声学波散射和电离杂质散射,在150~250 K温度范围内,更符合多种散射机构共同作用的散射机制。进一步拟合载流子浓度p与1/T的关系,计算获得晶体中杂质电离能ΔE_(A)=0.3042 eV。

CsPbBr_(3)纳米晶电子辐照效应研究

钙钛矿材料具有优异的光学性能和较高的载流子迁移率,成为空间太阳能电池领域极具竞争力的材料。然而空间粒子辐照容易改变材料结构和光学性能,导致其性能下降。为了探究电子辐照对CsPbBr_(3)材料结构与光学特性的影响规律,本文开展了CsPbBr_(3)材料电子辐照实验,利用高分辨透射电子显微镜表征CsPbBr_(3)纳米晶微观形貌,并通过X射线衍射分析和X射线光电子能谱分析进一步探究晶体结构的变化趋势。研究发现:电子辐照后CsPbBr_(3)纳米晶形貌变得粗糙,尺寸明显减小,并且纳米晶在高剂量电子辐照下变得紧凑,形成纳米团簇。其次,通过稳态紫外-可见吸收光谱图与光致发光谱图表征CsPbBr_(3)材料的光学性能,并利用第一性原理计算分析辐照后晶格膨胀带来的带隙变化。研究证明电子辐照后纳米晶颜色加深,影响钙钛矿的透光率,进而增强了样品对光的吸收性能,同时电子辐照能够分解CsPbBr_(3)纳米晶,特别是高剂量辐照后其光致发光性能降低了53.7%~78.6%。本文研究结果为钙钛矿纳米晶空间辐射损伤机理及应用研究提供了数据支撑。

Centimeter-sized Cs_(3)Cu_(2)I_(5)single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high-quality X-ray imaging

Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

Fe-3%Si大尺寸合金单晶的制备及磁感系数的计算

以取向Fe-3%Si合金热轧板为原材料,采用二次再结晶法制备了尺寸大于200 mm的合金单晶。随机选取3个单晶样品剪切成7个与轧向成不同角度、尺寸为50 mm×50 mm的样品,分别对所选样品进行单晶定向,并对每个样品的横、纵向磁性能进行了测量。以单晶定向结果为依据,计算每个单晶在晶体学坐标架下的极角和辐角,提出了一种单晶磁感系数的计算方法,并基于该方法以单晶磁性能实测值及其在晶体学坐标架下的极角和辐角为输入条件,测算了Fe-3%Si合金单晶磁感应强度系数并验证了其可靠性。采用该方法对{110}晶面平行于板面的任意方向单晶的磁感应强度进行了计算,为开展多晶材料磁性能计算提供了理论依据。

Kinetics and microstructural evolution during recrystallization of a Ni_3Al-based single crystal superalloy

The recrystallization kinetics and microstructural evolution of a Ni3Al-based single crystal superalloy were presented, especially the different recrystallization behaviors between the dendrite arm and the interdendritic region. The single crystal alloy was deformed by grit blasting. A succeeding annealing under inert atmosphere at 1280 ℃ for different time led to the formation of recrystallized grains close to the grit blasting surface. It was found that the recrystallization depth and velocity in the dendrite arm were respectively deeper and faster than those in the interdendritic region where the Y-NiMo phase existed. The recrystallization process in the interdendritic region was significantly inhibited by the Y-NiMo precipitates. However, the pinning effect gradually weakened with the annealing time due to the dissolution of the Y-NiMo phase, and the recrystallization depth in the dendrite arm was deeper than that in the interdendritic region.

Efficient Near-Infrared Quantum Cutting in Tm3＋/yb3＋ Codoped LiYF4 Single Crystals for Solar Photovoltaic

Downconversion （DC） with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium （Tm3＋） and ytterbium （Yb3＋） codoped yt- trium lithium fluoride （LiYF4） single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from yb3＋： 2Fs/2--＋2FT/2 transition, which was originated from the DC from Tm3＋ ions to Yb3＋ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm3＋ to Yb3＋ was an electric dipole-dipole interaction. The max- imum quantum cutting efficiency approached with 0.49mo1% Tm3＋ and 5.99mo1% Yb3＋. increasing the energy efficiency of crystalline energy part of the solar spectrum. up to 167.5% in LiYF4 single crystal codoped Application of this crystal has prospects for Si solar cells by photon doubling of the high

Lu^(3+)掺杂Na_(5)Y_(9)F_(32)∶Ho^(3+)/Yb^(3+)/Ce^(3+)单晶体的增强红色上转换发光与光学温度传感性能

采用密封的坩埚下降法技术生长了一系列Lu^(3+)(摩尔分数0、0.6%、1.2%、1.8%)掺杂Na_(5)Y_(9)F_(32)∶Ho^(3+)/Yb^(3+)/Ce^(3+)单晶体。在980 nm LD激发下,观察到单晶体的绿光543 nm(^(5)S_(2)/^(5)F_(4)→^(5)I_(8))、红光656 nm(^(5)F_(5)→^(5)I_(8))以及近红外750 nm(^(5)S_(2)/^(5)F4→^(5)I_(7))上转换发光。从上转换发光强度随激发光强度的变化情况,确定了543 nm、656 nm与750 nm的发光为双光子跃迁过程。研究了Lu^(3+)离子掺杂浓度对其发光强度与荧光寿命的影响情况,随着Lu^(3+)掺杂浓度从0增加到1.8%,单晶体中的656 nm红光逐步增强,543 nm绿光与750 nm近红外光随之减弱,红绿光强度比从0.01增加到了1.55,而543 nm荧光寿命从1.29 ms降低至0.99 ms。Lu^(3+)离子的掺入取代Y^(3+)晶格位,改变了单晶体的局域场环境,导致上转换发光强度的变化。基于随温度变化的上转换红光656 nm(^(5)F5→^(5)I8)与绿光543 nm(^(5)S_(2)/^(5)F4→^(5)I8)的发光强度变化,研究了1.8%Lu^(3+)掺杂Na_(5)Y_(9)F_(32)∶Ho^(3+)/Yb^(3+)/Ce^(3+)单晶体在298~448 K范围内的绝对灵敏度和相对灵敏度最大值分别为0.242%·K^(-1)和0.217%·K^(-1)。

GaFeO_(3)∶Mg晶体的生长及磁学性能研究

本文利用光学浮区法生长出了直径为7 mm的铁电单晶Mg_(x)Ga_(1-x)FeO_(3)(x=0.02、0.05、0.07和0.10),研究了Mg^(2+)对GaFeO_(3)(GFO)晶体饱和磁化强度和磁性转变温度的作用。通过XRD测试了晶体的结构和物相,结果显示,所有制备的晶体样品对应标准晶体卡库GFO(PDF#76-1005)的衍射特征,无其他杂相出现。XRD精修结果表明,该晶体结构为正交结构,空间群为Pna 2_(1),晶格常数和晶胞体积随着Mg^(2+)掺杂量的增加,呈现先增加后减小的趋势。通过综合物性测量系统研究了晶体的磁性能,结果表明,磁性转变温度和饱和磁化强度随着Mg^(2+)掺杂量的增加,同样呈现先增加后减小的趋势。当Mg^(2+)掺杂量x=0.07时,磁性转变温度和饱和磁化强度达到最大,分别为187.82 K、8.75 emu/g,达到了掺杂改性的目的。

Low field induced giant anisotropic magnetocaloric effect in DyFeO_3 single crystal

We have investigated the anisotropic magnetocaloric effect and the rotating field magnetic entropy in Dy FeO3 single crystal. A giant rotating field entropy change of -ΔSM^R = 16.62 J/kg·K was achieved from b axis to c axis in bc plane at 5 K for a low field change of 20 k Oe. The large anisotropic magnetic entropy change is mainly accounted for the 4 f electron of rare-earth Dy^3＋ ion. The large value of rotating field entropy change, together with large refrigeration capacity and negligible hysteresis, suggests that the multiferroic ferrite Dy FeO3 singlecrystal could be a potential material for anisotropic magnetic refrigeration at low field, which can be realized in the practical application around liquid helium temperature region.

Fracture Mechanics,Crack Propagation and Microhardness Studies on Flux Grown ErAlO_3 Single Crystals

Results on fracture mechanics and crack propagation have been obtained, making use of Vickers microhardness studies on two different crystallographic planes [(110) and (001)] of flux grown erbium aluminate crystals in the load ranging from 10-100 g. The variation of microhardness with load which is best explained by Hays and Kendall's law leads to the load independent values of hardness. Classification of cracks is dealt with and it is reported that the transition from Palmqvist to median types of cracks occurs at higher loads. The values of fracture toughness (K_C), and brittleness index (B_i) are calculated using median types of cracks.

Effect of temperature on photoresponse properties of solar-blind Schottky barrier diode photodetector based on single crystal Ga_2O_3

A solar-blind photodetector is fabricated on single crystal Ga_2O_3 based on vertical structure Schottky barrier diode. A Cu Schottky contact electrode is prepared in a honeycomb porous structure to increase the ultraviolet(UV) transmittance.The quantum efficiency is about 400% at 42 V. The Ga_2O_3 photodetector shows a sharp cutoff wavelength at 259 nm with high solar-blind/visible(= 3213) and solar-blind/UV(= 834) rejection ratio. Time-resolved photoresponse of the photodetector is investigated at 253-nm illumination from room temperature(RT) to 85.8℃. The photodetector maintains a high reversibility and response speed, even at high temperatures.

大尺寸CH_(3)NH_(3)PbBr_(3)晶体生长和光电性能表征

卤化物钙钛矿材料作为一种新型的半导体材料,具有材料廉价和光电转换性能优异的优点,基于该材料的各类光电器件已经开始逐步应用。虽然多晶薄膜仍然是主要的研究方向,但其具有形态无序、杂质较多的缺点,而单晶具有无晶界、低缺陷的特点,因此基于大尺寸单晶的研究开始被广泛关注。本文设计了一套内外反控温循环过滤生长装置,采用逆温结晶和籽晶相结合的方法制备了直径大于60 mm的CH_(3)NH_(3)PbBr_(3)单晶,对晶体样品进行了物相、微观形貌、光学和电学性能的研究。该晶体属于立方晶系,空间群为Pm3m;紫外-可见吸收光谱显示吸收截止边约为576 nm,荧光发射谱峰值552 nm;摇摆曲线显示晶体(100)晶面半峰全宽为91.42″。切割抛光后的晶片光响应灵敏,开关比为2.4×10^(3)。

Surface recrystallization of a Ni_3Al based single crystal superalloy at different annealing temperatures and blasting pressure

The effects of annealing temperature and grit blasting pressure on the recrystallization behavior of a Ni3Al based single crystal superalloy were studied in this work. The results show that the precipitation of the Y-NiMo phase occurs at 900 and 1000 °C, which precedes recrystallization. The initial recrystallization temperature was between 1000 and 1100 °C. Cellular recrystallization was formed at 1100 and 1200 °C, which consisted of large columnar γ′ and fine γ + γ′. The dendrite arm closed to the interdendritic region may act as nucleation sites during initial recrystallization by a particle simulated nucleation mechanism at 1280 °C. The size of the grains first turned large and then became small upon the pressure while the recrystallization depth increased all the time.

溶液法生长大尺寸CsCu_(2)I_(3)钙钛矿单晶及其光学性能研究

近年来,铜基钙钛矿因其出色的稳定性和环境友好性在发光和闪烁等领域受到了广泛关注。然而,目前对CsCu_(2)I_(3)晶体材料的研究主要集中在0维和1维领域,这限制了人们对材料本征性质和各向异性的深入理解,也限制了其在闪烁体中的实际应用。本文通过溶液降温法开展了CsCu_(2)I_(3)体块单晶的生长工艺研究,成功得到了长度达5 mm的高质量CsCu_(2)I_(3)单晶,该晶体无色透明、棱角分明、显露面完整。XRD测试结果表明,CsCu_(2)I_(3)晶体在经过6个月后依然保持了良好的稳定性;吸收光谱显示该晶体在310 nm波段具有明显的吸收峰,计算得到其禁带宽度为3.42 eV,表明CsCu_(2)I_(3)晶体属于宽禁带半导体;发射光谱显示该晶体发射波长位于580 nm处,半峰全宽为75 nm,绘制CIE色度图得到其发光色度坐标为(0.47,0.50),位于黄光区域,属于暖白色调(色温3000 K),这与该晶体在紫外灯照射下发出黄色荧光的现象一致;CsCu_(2)I_(3)晶体的荧光寿命测得为51.6和215.5 ns。

Extremely fast vortex dynamics in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrip

The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We here demonstrate exfoliations and nano-fabrications of Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips,which possess a rather weak pinning volume of vortices,relatively low resistivity,and large normal electron diffusion coefficient.The deduced vortex velocity in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips can be up to 300 km/s near the superconducting transition temperature,well above the speed of sound.The observed vortex velocity is an order of magnitude faster than that of conventional superconducting systems,representing a perfect platform for exploration of ultra-fast vortex matter and a good candidate for fabrications of superconducting nanowire single photon detectors or superconducting THz modulator.

电纺丝制备磁性单晶BiFeO_(3)纳米纤维并用于Cr(VI)的可见光催化还原

本工作提出一种将溶胶凝胶与静电纺丝结合的分步快速烧结技术,成功制备了单晶BiFeO_(3)纳米纤维。通过热重差热分析(TG-DTG)、XRD、SEM、TEM、EDS、紫外可见漫反射光谱和氮气吸附脱附曲线等测试对所制备材料的结构和形貌进行表征。同时,考察了BiFeO_(3)纳米纤维在可见光下对水中Cr(VI)的光催化还原性能。结果显示,相比于传统方式制备的纳米颗粒,该材料因更大的比表面积而具有更高的光催化活性。空穴消耗剂酒石酸的加入能够促进该材料对Cr(VI)的光催化还原反应,使还原效率提高87%。总之,本文制备的BiFeO_(3)材料能在可见光下响应,并在常温下具有弱磁性,能通过磁场力回收,在环境净化领域具有广阔的应用前景。

Optical Spectroscopy of Pr3+ Ion Singly Doped LiLuF4 Single Crystal by Bridgman Method

High quality LiLuF4 single crystals doped with various Pr3+ ions were synthesized by a vertical Bridgman method in completely sealed platinum crucibles. The excitation spectra spans from 420 nm to 500 nm. The prepared single crystals exhibit a blue band at 480 nm(3P0→3H4), a green band at 522 nm (3P1→3H5), and a red band at 605 nm (1D2→3H4)when excited at 446 nm;their corresponding average lifetimes are 38.5μs, 37.3μs, and 36.8μs, respectively, which are much longer than those in oxide single crystals. The effects of excitation wavelength and doping concentration on emission intensities and chromaticity coordinates are investigated. The optimal Pr3+ concentration is confirmed to be 0.5%.The temperature dependent emission shows that the emission intensity constantly decreases with the increase of temperature from 298 K to 443 K due to the enhancement of nonradiative quenching at high temperature. The 3P0→3H4 transition is the most vulnerable to temperature, followed by the 3P1→3H5 transition and 1D2→3H4 transition.

Identification and characterization of single crystal Bi_(2)Te_(3-x)Se_(x) alloy

The results of experimental investigation of n-type semiconductor based on Bi2Te3 alloy were presented. This material is used in manufacture of thermoelectric coolers and electrical power generation devices. BizTe2.88Se0.12 solid solution single crystal has been grown using the Czochralski method. Monitoring of structure changes of the sample was carried out by electron microscope. The elemental composition of the studied alloy was obtained by energy dispersive spectrometry （EDS） analysis and empirical formula of the compound was established. X-ray diffraction analysis confirmed that the Bi2Te2.88Se0.12 sample was a single phase with rhombohedral structure. The behavior upon heating was studied using differential thermal analysis （DTA） technique. Changes in physical and chemical properties of materials were measured as a function of increasing temperature by thermogravimetric analysis （TGA）. The lattice parameters values obtained by X-ray powder diffraction analyses of Bi2Te2.88Se0.12 are very similar to BizTe3 lattice constants, indicating that a small portion of tellurium is replaced with selenium. The obtained values for specific electrical and thermal conductivities are in correlation with available literature data. The Vickers microhardness values are in range between HV 187 and HV 39.02 and decrease with load increasing. It is shown that very complex process of infrared thermography can be applied for characterization of thermoelectric elements and modules.

BaTiO_(3)纳米单晶薄膜在外加电场作用下畴结构演化的相场研究

铁电薄膜的工作电场加载频率及基底失配应变可影响微观畴结构形态和材料宏观铁电性能。本文利用相场模拟方法分别研究了在-0.1%、-0.7%的失配应变下,0.1~100 kHz频率范围内BaTiO_(3)纳米单晶薄膜的铁电性能变化规律。研究发现,随着外加电场频率的增大,薄膜电滞回线由四方形向椭圆形转变,标准蝶形曲线向腰果形曲线发生改变。在50 kHz以下的低频段,矫顽场随频率增加而快速升高,但剩余极化强度变化幅度不大;而在50 kHz以上的高频段,矫顽场随频率增加略有升高,剩余极化强度则呈下降趋势。在低频段下铁电性能的频率依赖性受失配应变的影响较大,而在高频段下则对失配应变不敏感。同时发现,压缩失配应变可导致剩余极化及矫顽场显著升高,而拉伸应变的效果相反。分析表明,BaTiO_(3)纳米单晶薄膜铁电性能的频率依赖性源自内部微结构演化速度与外电场施加速率的相互竞争。本研究可为铁电功能薄膜材料的实验设计提供理论基础,为其在高频电子器件中的应用提供有力支撑。