富钇稀土-铝合金制取的研究Study on Preparation of Yttrium-Rich RE-Al Alloys

我国江西龙南稀土矿是目前世界上储量最大的富钇稀土矿、研制具有多种用途的钇（Y）-铝（Al）或富钇混合稀土（Ymm）-铝中间合金，对于开拓我国龙南稀土矿的应用领域扩大稀土合金出口具有重要意义。基于这一背景并针对目前氟化物体系制取Ymm-Al合金时存在着电解温度高，腐蚀现象严重，电效偏低等缺点，本文系统开展了在氯化物熔盐体系中电解制取Ymm-Al合金的研究工作。本工作由三部分组成：在第一部分工作中，开展了熔盐电解所需要基本原料-无水稀土氯化物制取的工艺研究。利用化学分析和结构分析手段，弄清了干法氯化过程中YmmCl_3水解的机理，提出了减弱水解的措施，即YmmCl_3先在850-900 ℃灼烧1.5 + 0.2hr，脱掉吸附水并将碱式碳酸盐转化为氧化物，增加稀土氧化物的比表面。通过条件试验得到最佳工艺条件为：采用NH_4 Cl:Ymm_2 O_3 = 14:1（摩尔比）的配料比，每次投入氯化装置的原料量为0.26 - 0.36 kg, 在400-450 ℃氯化反应激烈开始后迅速降温至400 ℃以下，待物料粘结现象消失后，再行升温氯化。出料及后期控制温在475 ± 25 ℃。经过3.8 ± 0.2hr氯化，可制得水不溶物小于1%并符合熔盐电解要求的YmmCl_3原料。此新工艺与原有干法工艺相比，流程短，装置简单，不需密闭抽真空，成本低，适于制取任何量的优质熔盐电解所需氯化稀土原料。在第二部分工作中，利用上述YmmCl_3原料，以液态铝为阴极，在氯化物体系中进行熔盐电解，通过试验得出在小型试验规模制取Ymm-Al合金的最隹工艺条件为：电解质组成（重量比）40%YmmCl_3-1%NaF-59%等摩尔的NaCl-KCl；电解温度为790 ± 5 ℃；阴极电流密为0.7 - 0.02A/cm~2；电解电量为333 ± 5库仑/克铝，制得钇铝合金中Ymm含量为10 ± 2%。添加1%的NaF可消除阴极表面生成枝状物，减少合金中夹渣和熔盐中沉渣。在电解工作中，将方差分析应用于试验数据处理，方差分析结果表明，各种试验因素对电效有明显影响，试验数据可靠，试验误差在允许范围以内。在第三部分工作中，利用线性扫描伏安法测定了在最隹电解工艺条件下Y~（3+）和Ymm在液态铝及钼电极上的析出电位。测定结果表明：Y~（3+）和Ymm~（3+）在液态铝阴极上的析出电位比在钼阴极上偏正0.2 ～ 0.8伏，氟离子的加入要比不加氟时析出电位不有同程度的负移，但考虑到氟离了具有消渣作用，加入少量氟比物添加剂对提高电效有利。

STUDY ON PREPARATION OF GAN AND COSI2 EPITAXIAL-FILMS BY MASS ANALYZED LOW-ENERGY DUAL ION-BEAM EPITAXY

The Mass Analyzed Low Energy Dual Ion Beam Epitaxy (MALE-DIBE) system has been designed and constructed in our laboratory. We believe that the system, which was installed and came into full operation in 1988, is the first facility of this kind. With our system we have carried out studies, for the first time, on compound synthesis of GaN and CoSi2 epitaxial thin films. RHEED and AES results show that GaN films, which were deposited on Si and sapphire substrates, are monocrystalline and of good stoichiometry. To our knowledge, GaN film heteroepitaxially grown on Si. which is more lattice-mismatched than GaN on sapphire, has not been reported before by other authors. RBS and TEM investigations indicated a rather good crystallinity of CoSi2 with a distinct interface between CoSi2 and the Si substrate. The channelling minimum yield chi(min) from the Co profile is approximately 4%. The results showed that the DIBE system with simultaneous arrival of two beams at the target is particularly useful in the formation of novel compounds at a relatively low substrate temperature.

Low -temperature preparation of ZnO films on Si substrates by MOCVD

ZnO films were deposited on Si（100） substrates at 300℃ by metal - organic chemical vapor deposition（MOCVD）. The effect of different ratios of DEZn to N2O on crystal quality was analyzed. It is found that the optimum ratio of DEZn to N2O is 2.1. And in this optimum growth condition, X - ray diffraction （XRD） and scanning probe morphology （SPM） images indicate that the films grow along the c - axis orientation. ZnO film exhibits a strong UV optical absorption near 388 nm. And the optical absorbance is close to zero,that indicates nearly 100% optical transparence. Photoluminescence （PL） spectrum shows only strong near - band - edge emissions with little or no deep - level emission related to defects. The full - width at half - maximum （FWHM） of the ultraviolet emission peak is 80meV. The results indicate that better crystal quality can be obtained.

Preparation of 50mm 3C-SiC/Si(111) as Substrates Suited for Ⅲ-Nitrides

50mm SiC films with high electrical uniformity are grown on Si(111) by a newly developed vertical low-pressure chemical vapor deposition (LPCVD) reactor.Both in-situ n- and p-type doping of 3C-SiC are achieved by intentional introduction of ammonia and boron into the precursor gases.The dependence of growth rate and surface morphology on the C/Si ratio and optimized growth conditions is obtained.The best electrical uniformity of 50mm 3C-SiC films obtained by non-contact sheet resistance measurement is ±2.58%.GaN films are grown atop the as-grown 3C-SiC/Si(111) layers using molecular beam epitaxy (MBE).The data of both X-ray diffraction and low temperature photoluminescence of GaN/3C-SiC/Si(111) show that 3C-SiC is an appropriate substrate or buffer layer for the growth of Ⅲ-nitrides on Si substrates with no cracks.

Preparation of Semi-Insulating Material by Annealing Undoped InP

Semi-insulating (SI) InP wafers of 50 and 75mm in diameter can be obtained by annealing of undoped liquid encapsulated Czochralski (LEC) InP at 930 ℃ for 80h. The annealing ambient can be pure phosphorus (PP) or iron phosphide (IP). The IP-SI InP wafers have good electrical parameters and uniformity of whole wafer. However, PP-SI InP wafers exhibit poor uniformity and electrical parameters, Photoluminescence which is subtle to deep defect appears in IP-annealed semi-insulating InP. Traps in annealed SI InP are detected by the spectroscopy of photo-induced current transient. The results indicate that there are fewer traps in IP-annealed undoped SI InP than those in as-grown Fe-doped and PP-undoped SI-undoped SI InP. The formation mechanism of deep defects in annealed undoped InP is discussed.

Preparation and characterization of erbium doped sol-gel silica glasses

Erbium-doped silica glasses were made by sol-gel process. Intensive photoluminescence (PL) spectra from the Er-doped silica glasses at room temperature were measured. A broadband peak at 1535 ma, corresponding to the I-4(13/2)-I-4(15/2) transition, its full width at half-maximum (FWHM) of 10 nm, and a shoulder at 1546 nm in the PL spectra were observed. At lower temperatures, main line of 1535 nm and another line of 1552 Mn instead of 1546 nm appear. So two types of luminescence centers must exist in the samples at different temperature. The intensity of main line does not decrease obviously with increasing temperature. By varying the Er ion concentration in the range of 0.2 wt% - 5wt%, the highest photoluminescence intensity was obtained at 0.2wt% erbium doped concentration. Luminescence intensity decreases with increasing erbium concentration. Cooperative upconversion was used to explain the concentration quenching of luminescence from silica glass with high erbium concentration. Extended X-ray absorption fine structure measurements were carried out. It was found that the majority of the erbium impurities in the glasses have a local structure of eight first neighbor oxygen atoms at a mean distance of 0.255 nm, which is consistent with the typical coordination structure of rare earth ion.

Preparation and photoluminescence of nc-Si/SiO2 MQW

The deposition rate and refractive index for a-Si(amorphous silicon) and SiO2 grown by PECVD were studied under different pressure, power and proportion of reactant source gases. a-Si/SiO2 MQW(multi-quantum well) with high quality was deposited under suitable conditions, in which the thickness of the a-Si layers is several nanometers. The sample of a-Si/SiO2 MQW was crystallized by laser annealing. Because of the confinement of the SiO2 layers, crystalline grains were formed during the a-Si layers were being crystallized. The size of the crystalline grains were not more than the thickness of the a-Si layers. The a-Si layers were crystallized to be nanometer crystalline silicon(nc-Si), therefore, nc-Si/SiO2 MQW was formed. For the a-Si/SiO2 MQW with 4.0nm a-Si wells separated by 5nm SiO2 barries, most of the a-Si were crystallized to silicon grains after laser annealing,and the size of the grains is 3.8nm. Strong photoluminescence with three peaks from the nc-Si/SiO2 MQW was detected at 10K. The wavelength of the peaks were 810nm, 825nm and 845nm, respectively.