Al掺杂Ⅷ型Sn基单晶笼合物载流子调制对其热电传输特性的影响

本文采用Sn自熔剂法,通过调节Ga的起始含量(Ba∶ Ga∶ Al∶ Sn =8∶x∶6∶50;x=10,20,30)实现对载流子进行调制,制备出具有p型和n型传导的Ⅷ型Sn基单晶笼合物,并对其结构和热电特性进行研究.研究结果表明,随着Ga起始含量的增加,Al在化合物中的固溶度减小,材料的晶格常数也随之减小;x=10的样品Seebeck系数全部为负值,x=30的样品Seebeck系数全部为正值,而x=20的样品在450 K后由于本征激发Seebeck系数显著降低,在550 K附近由p型传导转变为n型传导;室温下具有p型传导的化合物具有较高的载流子浓度,但其迁移率显著降低,从而导致其相应的化合物具有较高的电阻率,因此通过对Ga起始含量的改变能够对化合物的载流子实现有效调控;此外,在300 ～600 K内均具有p型传导的样品室温下的载流子有效质量较n型样品的高;通过估算的热导率κ、实测电阻率和Seebeck系数,计算出x=30的p型单晶样品在457 K处获得最大ZT值0.86.     

Tb掺杂CaMnO3氧化物材料热电输运性能的研究

采用溶胶-凝胶法结合陶瓷烧结工艺制备了Tb掺杂CaMnO3基氧化物热电材料,系统研究了Tb掺杂材料物相组成、微观组织和和电输运性能.结果表明,Tb掺杂试样均为单一物相的CaMnO3晶体材料.随着Tb掺杂量的增加,试样晶粒逐渐细化.所得CaMnO3基材料内部晶粒互连,试样结构较为致密.所有Tb掺杂试样电阻率随温度升高而降低,呈明显的半导体传输特性,其中Tb掺杂量为0.14的试样电阻率最低.Tb掺杂试样Seebeck系数绝对值随掺杂量的增加而降低,这是由于Tb掺杂引入的电子型载流子造成的.所有试样功率因子均随温度升高而逐渐增加,并且所有Tb掺杂试样的功率因子均大于未掺杂试样.其中Tb掺杂量为0.08的块体试样功率因子在测试温度最高点973 K时达到最大值2.0×10-4 W·m-1·K-2,远高于未掺杂试样,通过稀土元素Tb掺杂可以优化CaMnO3基过渡金属氧化物材料的电性能.     

Sn自溶剂含量对Al掺杂Ⅷ型Sn基单晶笼合物电传输特性的影响

通过Sn自熔剂法制备了Al掺杂Ⅷ型Sn基单晶笼合物Ba8Ga10Al6Snx(x=40,50,60;Sn40,Sn50,Sn60),并研究Ba8Ga10Al6Snx单晶笼合物的结构和电传输特性对自熔剂Sn初始含量的依赖性.结果表明,Al的实际含量随Sn自熔剂含量的增加而基本保持不变,说明Sn的起始含量对Al在该笼合物中固溶度的影响较小;室温下Sn60样品的载流子浓度较高,这可能是因Al在笼合物Ga8 Ga16Sn30中的占位不同而导致费米能级附近能带色散关系发生变化所引起;另一方面,在300～600 K的温度范围内,获得较高功率因子的是Sn初始含量为50的样品,在488 K处获得最大值1.82×10-3 W·m-1·K-2;获得较低功率因子的是Sn初始含量为40的样品,而功率因子较低主要是由于该样品电导率较低.     

Bi掺杂量对Mg-Si-Sn-Bi材料热电性能的影响

利用粉末冷压成型及真空烧结制备了不同Bi掺杂量的Mg-Si-Sn-Bi材料,并对制备材料组成和热电性能进行研究.结果表明,制备材料由Mg2Sn、Mg2Si和Mg2(Si,Sn)固溶体相组成.随测试温度的增加,制备材料的电阻率都急剧减小,这是典型的半导体特征.在研究范围内,掺杂Bi元素含量增加,制备材料的电阻率开始逐渐减小,但Bi掺杂量增加到一定值后,材料的电阻率又增加,而且掺杂后的材料电阻率都低于未掺杂的.制备材料的Seebeck系数是负值,表明这些材料都为n型半导体.对于掺杂Bi的材料,随着测试温度由室温增加到730 K,测得的Seebeck系数绝对值开始时轻微增加,约在240～270 K达到最大值,再随着温度增加,Seebeck系数绝对值又显著单调减小.对于掺杂Bi元素的材料,随Bi掺杂量的增加,Seebeck系数的绝对值先减少后增加,这是掺杂造成载流子浓度增加和散射过程加大相互竞争的结果.掺杂Bi的Mg-Si-Sn材料的功率因子都高于未掺杂的材料,且Bi掺杂量增加,制备材料的功率因子显著增加.对于1.29at; Bi和1.63at; Bi掺杂量的材料,功率因子分别在500 K和530 K存在一个极大值.     

灰锡自溶剂法Ba/Eu复合填充Ⅷ型Sn基单晶笼合物的制备及电传输特性

采用灰锡自溶剂法制备Ⅷ型Sn基单晶笼合物,并通过Eu对其进行掺杂.研究表明所制备样品均为空间群为I(4)3m的p型Ⅷ型Sn基单晶笼合物,Eu原子趋于取代Ba原子,且随着Eu元素起始含量的增加,材料晶格常数减小,熔点升高,较低的载流子浓度与较高的载流子迁移率使得材料Seebeck系数与电导率都有所提升,Eu起始含量x =0.50的样品其ZT值在480 K处获得最大值0.87.     

水热合成Zn_(0.9)Ni_(0.1)O稀磁半导体粉体

采用水热法,以3 mol/L的KOH作为矿化剂,在260℃下,保温24 h左右,进行Ni掺杂(x=0.1 mol),合成Zn1-xNixO稀磁半导体晶体。XRD测试表征以KOH作为矿化剂能够制备出发育良好的Zn0.9Ni0.1O稀磁半导体晶体,没有其它杂质相的产生。通过UV/Vis测试进一步说明掺杂的效果,掺杂使ZnO的禁带宽度降低至3.18 eV。FE-SEM测试显示所制备的晶体呈现长柱状。VSM测试表明,所制备的样品Zn0.9Ni0.1O在室温下表现出铁磁性。文章采用水热法制备出了具有铁磁性能的稀磁半导体粉体。     

超声喷雾热解法制备稀磁掺杂ZnO薄膜的研究

近年来,基于ZnO稀磁半导体在自旋电子器件方面的潜在应用价值,过渡金属掺杂的ZnO材料被广泛研究.但由于p型ZnO材料的制备非常困难,获得具有室温以上居里温度的Mn掺杂p型ZnO基稀磁半导体仍然是个难题.在N-In共掺杂成功实现ZnO薄膜p型掺杂的前期研究基础上,本研究采用超声喷雾热解(USP)法在Si基底上制备了Zn1-x,MnxO系列薄膜样品.X射线衍射表明所有ZnO薄膜样品都具有纤锌矿结构,没有发现其他物相的衍射峰存在.薄膜形貌研究发现,样品中的颗粒分布均匀.磁性测量表明N-Mn-In掺杂的样品显示出室温铁磁性.对N-Mn共掺杂和N-Mn-In掺杂的样品进行热处理后,发现薄膜的铁磁性能与薄膜中的空穴载流子具有直接的关联,这一现象与Mn掺杂的p型ZnO会显示室温铁磁性的理论预测是一致的,并用束缚磁性极化子模型解释了ZnO薄膜的铁磁性来源.     

不同掺杂量对水热合成Zn1-xNix O稀磁半导体粉体的影响

本文主要考虑不同掺杂量对水热合成Zn1-xNixO稀磁半导体粉体的影响.采用水热法,以3 mol/L NaOH作为矿化剂,在240℃下,保温24 h左右,进行Ni掺杂(x=0.05,0.1,0.2),合成Zn1-xNixO稀磁半导体晶体.XRD、FE-SEM测试表征晶体的物相组成和晶体形貌,XRD表明所制备的zn0.95Ni0.05O稀磁半导体晶体发育比较完整.通过UV-vis测试进一步说明掺杂的效果.VSM测试表明,所制备的样品在室温下有良好的磁滞回线,表现出铁磁性.     

衬底温度对磁控共溅射制备的Zn(O,S)薄膜结构和光电性能的影响

采用磁控共溅射沉积法,以氧化锌和硫化锌为靶材,在不同衬底温度下制备了Zn(O,S)薄膜.采用X射线衍射仪、原子力显微镜、紫外-可见-近红外分光光度计、霍尔测试仪和拉曼光谱测试仪对Zn(O,S)薄膜进行了结构和光电特性研究.结果表明:Zn(O,S)薄膜具有六方纤锌矿结构,属于二模混晶;在可见-近红外波段的吸收率小于5;;其为N型半导体,电学特性随衬底温度的变化而变化;衬底温度为200℃时制备的厚度为167 nm的Zn(O,S)薄膜的载流子浓度达到8.82×1019 cm-3,迁移率为19.3 cm2/V·s,表面呈金字塔结构.     

Sr3YCo4-xMgxO10.5+δ(0≤x≤0.04)多晶的制备和热电输运性质研究

采用固相反应法制备Sr3YCo4-xMgxO10.5+δ(0≤x≤0.04)系列多晶,研究了Mg掺杂对体系结构、电输运和热电性质的影响.结果表明系列多晶为四方晶系,由于掺入的Mg2+(0.066 nm)部分替代了Co3+/4+(0.053 nm/0.061 nm),使晶格膨胀;多晶热电势在340~830 K随温度升高而下降,且Mg掺杂对热电势影响不大,表明Mg掺杂对体系载流子浓度影响不大;多晶电阻率在100~300 K随温度升高而降低,且随着掺杂量增加电阻率降低,结合扫描电镜观察到多晶的气孔数目减少、晶粒连接紧密和热电势的结果认为Mg掺杂对体系电输运性质的影响机制主要是使气孔、晶界散射作用减弱、载流子迁移率变大,而Mg掺杂对载流子浓度的影响是次要的.     

Herstellung und elektrische Eigenschaften von dotiertem ZnSiP2

The properties of ZnSiP₂ crystals prepared by adding of Ga and In to the melt differ essentially from that of undoped samples. Especially the activation energies determined from the temperature dependence of the Hall coefficient prove that in both cases a real doping with shallow impurities has taken place. Ga and In act as donors suggesting the conclusion that Ga and In atoms substitute Zn atoms. The existence of strong electrical inhomogenities in a part of the samples is discussed.     

Effects of post-annealing on electrical properties of amorphous Ga-doped Zn–Sn–O semiconductor films

We investigated the effect of post-annealing on the electrical properties of amorphous gallium-zinc-tin oxide (a-GZTO) films with different Ga contents. The films were deposited at room temperature by sputtering and annealed in air for 1 h. It was found that the doping with Ga, which acts as the carrier suppressor, contributes to the thermal stability of characteristic properties of a-GZTO thin films. The film with a small amount of Ga showed significant variations in carrier concentration according to the annealing temperature. Increases in carrier concentration and mobility can be ascribed to the reduction of subgap density of states by annealing. After annealing at 400 °C, however, the enrichment of Zn cations in surface region resulted in considerable changes in chemical bonding states and consequently, the carrier concentration decreased by two orders of magnitude for the low Ga-doped ZTO film.     

Structural,optical and electrical properties of Ga-doped and (Ga,Co)-codoped ZnO films

The Ga-doped and (Ga, Co)-codoped ZnO films were grown on quartz glass substrate by inductively coupled plasma enhanced physical vapor deposition. The effect of Co doping and oxygen pressure on the structural, optical, electrical and magnetic properties of the as-grown films was investigated. The structural characterization revealed that high-quality films were grown with wurtzite structure and c-axis preferred crystalline orientation. The surface morphology was affected by Co doping and oxygen pressure. Room-temperature ferromagnetism was observed in (Ga, Co)-codoped ZnO films. We found that the optical and electrical properties were degraded with Co doping. The Ga-doped ZnO films had an average transmittance of above 88% in the visible wavelength, while (Ga, Co)-codoped ZnO showed a lower average transmittance (∼65%) due to the d-d transitions of Co²⁺. The resistivity and Hall mobility of (Ga, Co)-doped ZnO samples were lower than those of Ga-doped ZnO films when grown at the same oxygen pressure.     

Zum Wachstum von AIII-BV-Verbindungen aus nichtstöchiometrischen Schmelzen (III) Untersuchungen zur Flächenmorphologie homoepitaktischer GaAs-Schichten

The morphology of a surface with the formation of GaAs-layers from Ga solutions is caused by the primary formation of characteristic holes. The reason for the origin of such holes is explained by small stresses resulting from small lattice mismatches.     

溶胶-凝胶法制备Zn3Ga2Ge2O10:Cr3+0.01,Pr3+0.03,Yb3+0.3纳米长余辉材料及其表面修饰的研究

以Ga(NO3)3·8H2O、Zn(NO3)2·6H2O、Pr(NO3)2·6H2O、GeO2、Yb(NO3)3·5H2O、Cr(NO3)2·9H2O为原料,采用溶胶-凝胶法合成了Cr3+,Pr3+,Yb3+共掺杂的Zn3Ga2Ge2O10长余辉纳米材料(PLNPs).利用XRD,SEM,激发发射图谱,余辉曲线测试确定1000℃煅烧,保温3 h时,基质Zn3 Ga2 Ge2 O10已形成.Yb3+掺杂百分比为0.3时,样品的发光性能最好.Zn3 Ga2 Ge2 O10:Cr3+0.01,Pr3+0.03,Yb3+0.3纳米长余辉材料在波长为267 nm的紫外线激发下发射出中心波长为745 nm的深樱桃红色光,此时晶粒粒径约为150 nm;随着Yb3+掺杂百分比的增加,晶粒粒径逐渐变小.通过FT-IR,Zeta电势,激光粒度测试,TEM及悬浮实验测试表明,PEG修饰PLNPs后,可观察到明显的核壳结构,水合粒径约为155 nm;水溶性大大增加,0.3 mg/mL的浓度下其悬浮时间超过48 h,这表明PEG包裹PLNPs成功.     

Molecular Organization of Porphyrin-Metal Complexes

Abstract

Tetraethyltetramethylporphyrin substituted at two facing meso positions by N-methylimidazolyl groupings and its metal complexes were prepared. The absorption spectra of Zn and Mg complexes showed a characteristic splitting of Soret band and red-shifts of Q-bands indicating the exciton interaction of porphyrins in a slipped cofacial arrangement, where each imidazolyl group in one metal porphyrin is coordinated to metals in the other porphyrin skeleton. Typical upfield shifts in the ¹H NMR spectra arising from such the stacking structure elucidated Zn and Mg complexes as a dimer and an oligomeric mixture, respectively. Bis(imidazolyl)substituted tetraethyltetramethyl-porphyrin was also prepared. It suggested the hydrogen bonded oligomer formation through imidazolyl-imidazolyl interactions in a columnar orientation.

Electric conductivities of films prepared from these compounds werecharacterized. In a same line with behaviors in solution, samples capable of π-stacking interaction with adjacent porphyrins via ligand-to-metal coordination or hydrogen bonding exhibited higher conductivities as well as lower activation energies for the thermal conduction. These behaviors are understood as due to the overlap of π-systems of one porphyrin with neighboring porphyrins.     

Ga assisted oxide desorption on GaAs(0 0 1) studied by scanning tunnelling microscopy

Native oxide removal on GaAs wafers under conventional thermal desorption causes severe surface degradation. Recently a new method of Ga assisted oxide removal has reported improved initial surface conditions. A precise dosing of Ga is required to optimise the oxide removal, however the effects of alternate temperatures on the desorption process effects the reaction kinetics. By using selected bias imaging, scanning tunnelling microscopy (STM) can be used to probe the underlying bulk whilst the native oxide is still present. Hence the effects of oxide removal on the surface can be identified during the native oxide desorption. By comparing Ga assisted oxide removal on both vicinal and off cut samples, the Ga adatom kinetics are shown to underpin the oxide removal process and a sample temperature in excess of 500 °C is necessary to optimise the procedure.     

Structure of acetato(meso-5,10,15,20-tetraphenylporphyrinato)gallium(III): Ga(tpp)(OAc)

The title compound, Ga(tpp)(OAc), crystallizes in the space group P2₁/n witha=10.628(2),b=16.176(2),c=20.750(2), Å, =92.64(2)°, andZ=4. The gallium atom has a squarepyramidal coordination geometry formed by the four nitrogen atoms of the porphyrinato group (Np) and the acetate ion. The geometry around the gallium center of the Ga(tpp)(OAc) molecule has Ga–O(1)=1.874(4) Å and average Ga–Np(porphyrin nitrogen)=2.056(4) Å. The acetate group is unidentately coordinated to the gallium (III) atom. Ga-71 NMR spectroscopy provides a complementary method for investigation of the acetate ligand. Combining the calculated value of _c, 29.0 ps, with the measured Ga-71 quadrupolar relaxation time, T_1Q=11.1 s, the quadrupole coupling constant of Ga-71 is 28.1 MHz. This further supports that Ga is covalently coordinated to the acetate and tpp in Ga(tpp)(OAc). The methyl and carbonyl carbons of the acetate group are separately located at 20.4 and 168.8 ppm at 24°C for the Ga(tpp)(OAc).     

Zur Lumineszenz von Zinksiliziumphosphid

Results of cathodoluminescene measurements of ZnSiP₂-single crystals grown by different techniques are reported. The luminescence excited in the various samples showed considerable differences in intensity and spectral position. These differences are apparently caused by the irregular incorporation of recombination centres in the present stage of crystal growth. Samples grown by “vapour phase technique with ZnCl₂” and by “spontaneous crystallisation from Sn or zn melt” showed line spectra typical for the special method of crystal growing. This relation between a typical line spectrum and the method of crystal growing chosen is attributed to the participation of intrinsic defects in the recombination processes. The detection of doping elements by means of luminescence measurements is discussed for ZnSiP₂ crystals doped by adding Te, Se, Ga. or In to the Zn melt.     

La3Ta0.5Ga5.5-xAlxO14高温压电晶体材料的声表面波特性研究

本文计算了La3Ta0.5Ga5.5-xAlxO14(x＝0,0.3,O.5)压电晶体的X,y和Z切型的声表面波速度、机电耦合系数及能流角.计算结果表明了La3Ta0.5Ga5.5-xAlxO14(LTGAx)具有声表面波速度低、机电耦合系数大、存在能流角为零的切型等优点,同时总结出y切型为声表面波特性比较好的切型,为LTGAx(x＝0,O.3,0.5)晶体的声表面波应用提供了理论依据.