喀斯特地区森林生态系统物质循环的锶同位素地球化学研究

钙是地壳中最丰富的碱土金属元素，同时也是所有植物生长所需要的常量营养元素。越来越多的证据表明Ca是影响森林生态系统结构和功能的重要因素。贵州地处典型喀斯特地区，也是我国酸雨重灾区之一。酸沉降可以导致土壤中盐基离子的流失并释放出具有植物毒性的元素，对森林生态系统造成破坏。在酸化土壤上，Ca的流失可以直接或间接地影响森林的生产力。在受到酸沉降影响的森林生态系统，Ca、Mg、K等植物生长所必须的常量营养元素将从土壤可交换态离子库中淋失。大气输入与岩石风化是森林生态系统K、Ca、Mg等碱基离子的主要来源，了解二者的输入比率及转化是研究森林流域内物质循环过程的关键。为了评估森林健康状况和酸沉降对森林生态系统的影响，识别并区分植物营养物质的不同来源是非常有必要的。 喀斯特地区森林生态系统是物质、能量交换复杂且快速的开放系统。本论文应用Sr同位素示踪方法研究了酸沉降对贵州省喀斯特地区森林小流域营养离子循环的影响。选择了一处典型的森林小流域，把“岩石－土壤－地表水－大气沉降－植物”作为一个完整的系统考虑，系统采集了大气降水、穿冠水、地表水、植被、土壤、岩石样品。利用化学质量平衡、锶同位素地球化学等研究手段，探讨了喀斯特森林小流域水循环过程中营养元素和锶同位素组成的时空变化，评判了酸沉降对土壤－植被系统中营养元素与锶同位素组成的影响，定量计算了大气沉降与土壤风化分别对森林植被营养物质来源的贡献率，并进行了微生物对矿物差异风化作用锶同位素示踪的探索性研究，揭示了喀斯特背景下森林生态系统营养物质来源、分布以及迁移转化规律，为喀斯特地区森林生态环境质量评价及其环境保护提供科学依据。主要结论如下： 1．龙里森林小流域降雨的pH显示改区属于受酸雨危害地区。从大气降水到地表水的转化过程中，水溶液中主要离子的浓度发生了较大的变化。在酸雨影响下，雨水对林冠主要表现为营养阳离子的淋失作用，阴离子除NO3-被叶片吸收外总体上也是表现为淋失作用。龙里森林小流域水溶液的锶同位素比值组成总体上受灰岩风化端元控制，水体的87Sr/86Sr的比值变化范围为0.70716～0.71051。大气降水、穿冠水、地表水等不同类型水溶液的锶同位素比值组成变化反映了水循环过程中水溶液与周围环境进行离子交换。 2．土壤中可交换态离子、碳酸盐岩结合态离子和全样的锶同位素组成之间在同一剖面存在较大的变化，且在土壤剖面垂向上也存在着较大的变化。黄壤剖面中不同赋存形式离子的锶同位素组成之间的变化较之石灰土剖面更为明显。可交换态离子的锶同位素比值变化特征可以很好地说明雨水对土壤的影响程度。黄壤剖面土壤可交换态离子的锶同位素比值在土壤剖面形成的垂向分布梯度，反映了雨水对土壤的影响可以达到130 cm深度。 3．喀斯特地区黄壤上生长的植物具有高钙含量的特征，营养元素含量具Ca > K > Mg特点。研究区植物Ca、K、Sr的平均含量均高出报道的陆生植物的平均含量, 但比贵州地区同样以灰岩为母质发育而来的石灰土上生长的植物低。石灰土上植物体内（包括皮、叶、根、茎）的Ca含量比黄壤上植物体内的高，而Sr、Ba、Mn含量则比黄壤上植物体内的低；阔叶树的营养元素含量一般大于针叶树的。 4．不同植物种所吸收的营养元素来源存在差异。基于锶同位素组成的端元模式计算结果表明，苔藓和石松吸收的营养阳离子主要来自大气沉降，苔藓可以达到 88.66%，石松则为77.28%。除了苔藓、石松外，喀斯特地区黄壤上植物生长所需的58.88%～85.64%的Ca、Mg来自土壤风化所产生的可交换态阳离子，大气输入部分所占份额相对较小。 5．土壤中可交换态离子的锶同位素比值是植物体的锶同位素组成的主要影响因素。植物叶片、韧皮、根等不同器官的87Sr/86Sr比值之间存在较大变化，并且树根的87Sr/86Sr比值随着土壤深度加大在垂向上产生变化，反映了植物器官对不同来源营养元素的利用效率存在差异。同样生长在龙里石灰土样地上的马尾松和光皮桦在树根的锶同位素垂向变化上有较大差别，这可能与其植物生理生态特性有关。老叶与新叶之间87Sr/86Sr比值则没有变化。 6．利用Sr同位素示踪方法能较好地区分混合体系中Ca2+等离子由不同矿物风化所释放的比例，进而定量分析微生物对矿物的差异风化作用。在磷灰石和方解石组成的混合体系中，随着微生物培养时间的延长，培养基上清液的87Sr/86Sr比值随时间变化，这反映出方解石与磷灰石两种矿物的微生物风化释放离子对培养液中Ca2+来源的相对贡献率发生改变。基于锶同位素组成的端元模式计算结果表明，黑曲霉组培养液中的Ca2+先由方解石风化所贡献，随后黑曲霉对方解石的风化作用减弱，此时，溶液中Ca2+主要来自磷灰石的风化；而青霉组培养液中的Ca2+先来自磷灰石的风化，随后来自方解石的风化。

中国南北方泥盆纪腕足化石碳、氧、锶同位素研究

海相碳酸盐岩C、O、Sr 同位素研究是地球化学重要的示踪手段之一。它可以为认识地质历史时期的气候变化，海水原始碳、氧、锶同位素组成，陆地和海洋生物盛衰的长期变化特征，以及碳、氧等元素的外生循环等一些重大的基础学科问题提供重要的依据。研究表明：腕足化石因具有较强抵抗成岩后生作用能力、分布广泛、便于操作等原因被认为是较为理想的研究样品之一。 本论文对来自中国南、北方泥盆纪不同沉积单元腕足化石碳、氧、锶同位素组成进行测试，探讨中国南、北方不同沉积单元腕足化石碳、氧、锶同位素差异。从地球化学角度对我国泥盆纪海平面变化，海洋生物盛衰、陆地风化强度以及构造运动研究进行诠释。 中国泥盆系沉积类型齐全，从南到北，分布着不同构造单元条件下沉积而成的地层。华南泥盆系属地台型稳定沉积类型，四川龙门山地区泥盆系形成于冒地槽构造单元中，而中国北方泥盆系为优地槽活动构造单元的产物。三类构造单元的地壳活动和火山活动不同，生活在其中的腕足壳体碳、氧、锶同位素组成是否存在差异？不同构造单元的海平面变化、海洋生物盛衰以及陆地风化强度是否不同。 研究中通过上述不同沉积单元腕足化石碳、氧、锶同位素组成详细研究，得出以下几点认识： 1) 在腕足化石保存鉴定过程中：微体结构实验显示南、北方剖面腕足化石壳体结构保存完整，有着明显的纤维层和棱柱层结构，但北方剖面腕足化石微裂隙较多，有着不少后期物质充填。在阴极灯照射下，南方剖面腕足化石基本不发光，仅因少量裂隙中后期物质充填有着微弱发光现象存在。北方剖面腕足化石基本上都有着轻微发光现象，尤其内蒙古地区腕足化石。微量元素Fe、Mn、Sr 含量及其Mn/Sr 值表明南、北方剖面腕足化石绝大多数符合腕足保存完好的标准。表明：南方剖面腕足化石保存完好，可以用于的碳、氧、锶同位素组成研究。北方剖面腕足化石保存程度较差，其同位素信息可能遭受成岩蚀变作用的影响，特别是容易遭受蚀变影响的氧同位素组成。 2) 成岩后生作用总是导致碳酸盐岩全岩样品中碳、氧、锶同位素组成发生变化，无法保存原始的同位素信息。腕足化石同碳酸盐岩全岩碳、氧、锶同位素对比表明：碳酸盐岩全岩样品中碳、氧同位素组成都低于腕足化石样品中同位素组成，锶同位素组成正好相反，但在不涉及定量化研究的前提下，碳、锶同位素基本上可以代表着地质历史时期碳、锶同位素变化趋势。也即是说可以利用碳酸盐岩全岩样品进行碳、锶同位素演化趋势研究。至于碳酸盐岩全岩样品中氧同位素组成，低于腕足化石氧同位素组成达 -2‰～-3‰。在目前常用于氧同位素古温度的研究中差异太大。因此，建议不要利用碳酸盐岩全岩样品中氧同位素组成进行古温度研究。 3) 碳同位素组成变化可以指示有机碳的埋藏情况。中国南、北方剖面腕足化石碳同位素研究表明：腕足化石中碳同位素组成基本上在 -2‰ ～ 4‰之间变化，北方剖面较低，南方剖面较高。其碳同位素Locfit 演化对比显示：北方剖面碳同位素演化同华南以及四川龙门山剖面中碳同位素演化有着许多相似之处，表明北方海域有机碳埋藏情况同南方海域有机碳埋藏情形基本一致。分析表明：四川龙门山以及华南剖面泥盆纪时期有着三次有机碳高速埋藏时期，可能受海平面变化以及与之有关的生物繁盛状况共同控制。至于北方剖面碳同位素组成相对较低，一方面可能由于腕足化石保存方面的原因，在成岩蚀变作用影响下北方剖面腕足碳同位素组成较低。另一方面，北方地区较多的火山活动，释放大量含有较多12C 的CO2，融入海水发生同位素交换，导致北方地区碳同位素组成较低。 4) 由于北方剖面存在遭受成岩蚀变作用影响的可能，北方剖面腕足化石壳体氧同位素平均组成(-11.75‰ ~ -21.13‰)明显低于四川龙门山剖面(-5.14‰ ~-7.20‰)、华南剖面(-4.35‰ ~ -10.31‰)氧同位素平均组成，无法对水岩反应控制海洋中氧同位素组成给出肯定的答案。但腕足化石保存完好的四川龙门山剖面和华南剖面氧同位素组成(氧同位素素组成埃姆斯阶为-7.20‰、-7.58‰；吉维特阶-5.62‰、-4.60‰；氟拉斯阶-5.18‰、-4.35‰)显示：优地槽沉积单元的龙门山海域同稳定地台沉积单元的华南海域氧同位素一致，甚至较低，表明水岩反应根本无法控制海洋中氧同位素组成。 5) 四川龙门山剖面下泥盆统埃姆斯阶氧同位素组成为 -9.9‰～-4.5‰，明显低于世界上其他地区同时期腕足化石的氧同位素组成，其差异达 -3‰~-4‰。微量元素Fe、Mn 的演化趋势以及氧同位素演化趋势显示：龙门山海域在埃姆斯阶时期同广阔海域之间海水交流不畅通，其氧同位素组成受淡水河流注入的影响。根据氧同位素古温度计估算(假定古海水δ18O 值为 -3‰SMOW)，姆斯阶时期温度高达52℃，远远超过生物所能生存的极限，印证龙门山海域埃姆斯阶氧同位素组成受淡水河流注入的影响。艾菲尔阶～氟拉斯阶，龙门山海域的温度为21℃ ～33℃，表明龙门山海域为典型的低纬地区热带气候。 6) 早泥盆纪时期，锶同位素比值较高，显示风化作用较为强烈；可能是由于加里东造山作用的影响，大量陆地的暴露，促进风化作用的进行。其后，锶同位素组成逐渐降低指示风化作用变弱。锶同位素降低可能由于海底扩展运动造成幔源锶的增加，同时引起海平面上升，引起陆地风化面积的减少，导致风化作用的减弱。幔源锶增加和陆源锶的减少，造成锶同位素比值的不断下降。早泥盆世晚期－中泥盆世，锶同位素组成显示风化作用(强度较低)和构造运动稳定。可能原因为在海平面较高时海侵－海退幅度较小，幔源锶和陆源锶之间达到均衡。中泥盆世后期，锶同位素组成显示：风化作用程度较强。可能由于该时期温度的缓慢上升，导致风化作用加强，陆源锶输入增多引起的。 7) 不同沉积单元腕足化石碳、氧、锶同位素对比表明：局部的区域环境对碳、氧、锶同位素有影响。在考虑利用不同剖面进行地质历史时期某时段碳、氧、锶同位素数据叠加构建完整同位素演化曲线时；对于碳同位素，相同沉积单元条件下，辨别出长时间变化和局部影响时可以应用于同位素演化曲线的构建。而不同沉积单元的碳同位素组成存在差异，不能应用于碳同位素曲线的构建。不同沉积单元氧同位素组成存在较大差异，相同沉积单元的氧同位素组成同样也存在较大差别，表明局部环境对氧同位素组成影响较大，氧同位素曲线的构建最好避免多个剖面的叠加。锶同位素比值，不同沉积单元在长期演化趋势上基本一致，在排除局部环境因素的影响下可以进行多剖面锶同位素演化曲线的构建。

赣江流域水化学特征与流域风化过程——主成分及锶同位素地球化学研究

对河流地球化学特征的研究可以获得有关流域化学风化以及化学元素在地球表生系统生物地球化学循环的相关信息。同时，流域风化作用是全球长期碳旋回及与其有关的环境效应的一个重要组成部分。我国学者对大流域的碳酸盐岩地区进行了大量研究，但硅酸盐地区的研究相对薄弱，研究指出：中国河流水的离子组成主要受碳酸盐风化作用和蒸发岩溶蚀作用的影响，受铝硅酸盐风化作用的影响不如前两者明显。硅酸盐岩的风化产物在一定程度上控制着地表水系的地球化学组成，因而对硅酸盐岩区河流的地球化学组成变化的研究，有助于我们了解硅酸盐岩地区的化学风化作用与水文地球化学特征的关系，以及控制河流水体地球化学组成变化的多种因素。赣江是长江的主要支流，在江西省国民经济、生态环境保护和社会生活中占有重要的地位。尤为重要的是，赣江流域广泛分布有硅酸岩岩石和土壤，是世界上硅酸岩连片分布的典型地区之一。由赣江水体和悬浮物携带输送的各类物质组分经鄱阳湖输入长江是全球元素地球化学循环的重要组成部分，对全球环境变化研究有重要意义。 本论文利用赣江流域物理化学参数、化学质量平衡和同位素地球化学研究手段，重点讨论赣江流域的水化学特征、主要离子来源，并探讨主要的化学风化反应。定量计算了流域化学风化侵蚀速率及其对大气CO2消耗的影响，探讨了河流水化学特征与人为活动、气候、地形、岩性等因素之间的关系。得出如下主要结论和几点新认识。 赣江流域河流受控于中亚热带湿润季风气候条件下，碳酸盐硅酸盐化学风化和人为活动的共同影响，以快速的碳酸盐和典型硅酸盐的化学风化共同侵蚀作用区别于其他地区河流。枯水期和丰水期样品中，阳离子中Na+和Ca+含量最高，其次是Mg2+，K+含量最低；阴离子中，Cl-，HCO3-占主导地位，SO42-次之，NO3-含量最低；溶解性硅的含量变化范围不大。赣江流域河水的化学组成反映了硅酸盐岩化学风化作用对河水化学组成控制的典型特征。 受赣江流域气候、岩性、地形和人为活动的影响，枯水期丰水期离子成分主要来源于岩石/土壤的化学风化。碳酸盐岩矿物风化与硅酸盐岩矿物相比是普遍而快速的，所以赣江流域风化很大程度上会受碳酸盐所支配。此外，人为输入影响与赣江流域发达的农业、工业生产产生污染相一致。 赣江流域HCO3-与Ca2+、HCO3-与Mg2+、SO42-与Mg2+、Na+与Cl-均存在明显的相关关系。Na+与SO42-、HCO3-与Si、Na+与Si、K+与Si不存在相关性或相关性不明显。赣江流域样品Si/(Na*+K)比值范围低，表明风化作用在表生环境中进行，风化作用中主要是富含阳离子的次生矿物。Si浓度受生物影响很小，主要是岩性的作用。 除了岩石风化溶解作用，赣江流域盆地区域降水量将直接影响地表径流和河流流量。河流流量对各主要离子浓度的影响顺序为HCO3->Ca2+>Mg2+>SO42- >Na+>Cl-，起到稀释作用。所以赣江流域河水特征受岩性和气候条件的共同作用。 赣江流域高的锶同位素比值（87Sr/86Sr）表明了赣江流域Sr来源的硅酸岩风化典型特征，丰水期河流溶解态Sr浓度有所下降。锶同位素为大气降水和岩石风化的混合型，并且辨别出两个碳酸盐硅酸盐是最主要的岩石风化溶解端元组分。 利用SPSS统计软件，对9个离子组分作为变量进行主成分分析（PCA）和因子分析，解析出主要影响因素。分析统计结果表明两类岩石和人为输入对河水溶解质的贡献率分别是：碳酸盐最大，其次是硅酸盐，人为活动输入最小。并定量的计算出碳酸盐、硅酸盐、大气CO2和人类活动对于赣江溶质组成的相对贡献率。根据径流量和流域面积，计算得到每年赣江流域岩石风化作用的大气CO2消耗分别为枯水期520.2×103mol/km2和丰水期383.4×103mol/km2，较强烈的碳酸盐风化溶解和明显的硅酸盐风化特征导致了赣江流域岩石风化作用的CO2消耗率高于世界平均水平。扣除大气CO2和人类活动输入的贡献后，估算得到赣江流域的年均化学风化率为30.3t/km2•a，在影响河流化学风化的众多因素中，地质和气候因素起着主导作用。赣江流域对于全球的大气CO2源汇效应是明显的汇项。

Fabrication and testing of a doped lanthanum gallate electrolyte thin-film solid oxide fuel cell

A supported lanthanum gallate (LSGM) electrolyte thin-film solid oxide fuel cell with Ni-YSZ cermet anode and strontium-doped lanthanum manganite (LSM)-yttria stabilized zirconia (YSZ) composite cathode was, for the first time, fabricated and tested. The cell was prepared by an unconventional approach, in which an LSGM thin film (about 15 mum thick) was first deposited on a porous substrate such as a porous YSZ disk by a wet process and sintered at a high temperature (above 1400degrees C). NiO was then incorporated into the porous substrate by a carefully controlled impregnation process and fired at a much lower temperature. In this way, the severe reaction between LSGM and NiO at a high temperature, which is required for the full densification of LSGM film, can be avoided. A strontium-doped LaMnO3 (LSM)-YSZ composite cathode was screen printed on the surface of the LSGM film and then fired at 1250degrees C. The electrolyte resistances of the SOFC single cells fabricated by this approach are much lower compared to those of thick LSGM film supported cells. A maximum output power density of over 0.85 W/cm(2) at 800degreesC with H-2 as fuel and air as oxidant for a fabricated cell was achieved. (C) 2002 The Electrochemical Society.

Environmental impacts of the coal ash spill in Kingston, Tennessee: an 18-month survey.

An 18 month investigation of the environmental impacts of the Tennessee Valley Authority (TVA) coal ash spill in Kingston, Tennessee combined with leaching experiments on the spilled TVA coal ash have revealed that leachable coal ash contaminants (LCACs), particularly arsenic, selenium, boron, strontium, and barium, have different effects on the quality of impacted environments. While LCACs levels in the downstream river water are relatively low and below the EPA drinking water and ecological thresholds, elevated levels were found in surface water with restricted water exchange and in pore water extracted from the river sediments downstream from the spill. The high concentration of arsenic (up to 2000 μg/L) is associated with some degree of anoxic conditions and predominance of the reduced arsenic species (arsenite) in the pore waters. Laboratory leaching simulations show that the pH and ash/water ratio control the LCACs' abundance and geochemical composition of the impacted water. These results have important implications for the prediction of the fate and migration of LCACs in the environment, particularly for the storage of coal combustion residues (CCRs) in holding ponds and landfills, and any potential CCRs effluents leakage into lakes, rivers, and other aquatic systems.

Radium and barium removal through blending hydraulic fracturing fluids with acid mine drainage.

Wastewaters generated during hydraulic fracturing of the Marcellus Shale typically contain high concentrations of salts, naturally occurring radioactive material (NORM), and metals, such as barium, that pose environmental and public health risks upon inadequate treatment and disposal. In addition, fresh water scarcity in dry regions or during periods of drought could limit shale gas development. This paper explores the possibility of using alternative water sources and their impact on NORM levels through blending acid mine drainage (AMD) effluent with recycled hydraulic fracturing flowback fluids (HFFFs). We conducted a series of laboratory experiments in which the chemistry and NORM of different mix proportions of AMD and HFFF were examined after reacting for 48 h. The experimental data combined with geochemical modeling and X-ray diffraction analysis suggest that several ions, including sulfate, iron, barium, strontium, and a large portion of radium (60-100%), precipitated into newly formed solids composed mainly of Sr barite within the first ∼ 10 h of mixing. The results imply that blending AMD and HFFF could be an effective management practice for both remediation of the high NORM in the Marcellus HFFF wastewater and beneficial utilization of AMD that is currently contaminating waterways in northeastern U.S.A.

Impacts of shale gas wastewater disposal on water quality in western Pennsylvania.

The safe disposal of liquid wastes associated with oil and gas production in the United States is a major challenge given their large volumes and typically high levels of contaminants. In Pennsylvania, oil and gas wastewater is sometimes treated at brine treatment facilities and discharged to local streams. This study examined the water quality and isotopic compositions of discharged effluents, surface waters, and stream sediments associated with a treatment facility site in western Pennsylvania. The elevated levels of chloride and bromide, combined with the strontium, radium, oxygen, and hydrogen isotopic compositions of the effluents reflect the composition of Marcellus Shale produced waters. The discharge of the effluent from the treatment facility increased downstream concentrations of chloride and bromide above background levels. Barium and radium were substantially (>90%) reduced in the treated effluents compared to concentrations in Marcellus Shale produced waters. Nonetheless, (226)Ra levels in stream sediments (544-8759 Bq/kg) at the point of discharge were ~200 times greater than upstream and background sediments (22-44 Bq/kg) and above radioactive waste disposal threshold regulations, posing potential environmental risks of radium bioaccumulation in localized areas of shale gas wastewater disposal.

Isotopic imprints of mountaintop mining contaminants.

Mountaintop mining (MTM) is the primary procedure for surface coal exploration within the central Appalachian region of the eastern United States, and it is known to contaminate streams in local watersheds. In this study, we measured the chemical and isotopic compositions of water samples from MTM-impacted tributaries and streams in the Mud River watershed in West Virginia. We systematically document the isotopic compositions of three major constituents: sulfur isotopes in sulfate (δ(34)SSO4), carbon isotopes in dissolved inorganic carbon (δ(13)CDIC), and strontium isotopes ((87)Sr/(86)Sr). The data show that δ(34)SSO4, δ(13)CDIC, Sr/Ca, and (87)Sr/(86)Sr measured in saline- and selenium-rich MTM impacted tributaries are distinguishable from those of the surface water upstream of mining impacts. These tracers can therefore be used to delineate and quantify the impact of MTM in watersheds. High Sr/Ca and low (87)Sr/(86)Sr characterize tributaries that originated from active MTM areas, while tributaries from reclaimed MTM areas had low Sr/Ca and high (87)Sr/(86)Sr. Leaching experiments of rocks from the watershed show that pyrite oxidation and carbonate dissolution control the solute chemistry with distinct (87)Sr/(86)Sr ratios characterizing different rock sources. We propose that MTM operations that access the deeper Kanawha Formation generate residual mined rocks in valley fills from which effluents with distinctive (87)Sr/(86)Sr and Sr/Ca imprints affect the quality of the Appalachian watersheds.

Stability of Sr adatom model structures for SrTiO3(001) surface reconstructions

We report results of first-principles calculations on the thermodynamic stability of different Sr adatom structures that have been proposed to explain some of the observed reconstructions of the (001) surface of strontium titanate (Kubo and Nozoye 2003 Surf Sci. 542 177). From surface free energy calculations, a phase diagram is constructed indicating the range of conditions over which each structure is most stable. These results are compared with Kubo and Nozoye's experimental observations. It is concluded that low Sr adatom coverage structures can only be explained if the surface is far from equilibrium. Intermediate coverage structures are stable only if the surface is in or very nearly in equilibrium with the strontium oxide.

Investigation of dead-layer thickness in SrRuO3/Ba0.5Sr0.5TiO3/Au thin-film capacitors

Thin-film capacitors, with barium strontium titanate (BST) dielectric layers between 7.5 and 950 nm in thickness, were fabricated by pulsed-laser deposition. Both crystallography and cation chemistry were consistent with successful growth of the BST perovskite. At room temperature, all capacitors displayed frequency dispersion such that epsilon (100 kHz)/epsilon (100 Hz) was greater than 0.75. The dielectric constant as a function of thickness was fitted, using the series capacitor model, for BST thicknesses greater than 70 nm. This yielded a large interfacial d(i)/epsilon (i) ratio of 0.40 +/-0.05 nm, implying a highly visible parasitic dead layer within the capacitor structure. Modeled consideration of the dielectric behavior for BST films, whose total thickness was below that of the dead layer, predicted anomalies in the plots of d/epsilon against d at the dead-layer thickness. In the capacitors studied here, no anomaly was observed. Hence, either (i) 7.5 nm is an upper limit for the total dead-layer thickness in the SRO/BST/Au system, or (ii) dielectric collapse is not associated with a distinct interfacial dead layer, and is instead due to a through-film effect. (C) 2001 American Institute of Physics.

Phase transitions in epitaxial Ba0.5Sr0.5TiO3 thin films

Ba0.5Sr0.5TiO3 (BST) thin-film capacitor structures with various thicknesses, (50-1200 nm) and different strain conditions (on lanthanum strontium cobalt oxide La0.5Sr0.5CoO3 and strontium ruthenate SrRuO3 buffer layers) were made using pulsed laser deposition, and characterized by x-ray diffraction. The out-of-plane lattice parameter was followed as a function of temperature within the 100-300 K temperature interval. The phase sequence (cubic-tetragonal-orthorhombic-rhombohedral) known to exist in the bulk analog is shown to be strongly affected by both the stress conditions imposed by the buffer layer and the thickness of the BST film itself. Thus, no phase transition was found for the in-plane compressed BST films. On the stress-free BST films, on the contrary, more phase transitions were observed. It appeared that the complexity of structural phase transitions increased as the film thickness in this system was reduced.

Studies of switching kinetics in ferroelectric thin films

Experimental studies are reported concerning the importance of interfacial capacitance (including electrode screening, space-charge layers, and/or chemically discrete dead layers). on domain switching behaviour in thin films of ferroelectric lead zirconate-titanate (PZT), strontium bismuth tantalate (SBT), and barium strontium titanate (BST). Emphasis is placed upon studies at applied field values very near the coercive field E, asymmetry in fatigue for positive and negative polarity coercive fields, and in the case of BST, of the coexistence of ferroelectric and paraelectric phases Studies of dielectric loss show important correlations between tan 6 and fatigue (polarization decrease) as a function of bipolar switching cycles N. This is a priori not obvious, since the former is a linear response and the latter, a nonlinear response. Modelling of enlarged interfacial,space-charge layers in PZT films and chemically distinct dead (paraelectric) layers in BST films shows contradictory tendencies of coercive-voltage changes with the growth of passive layers.

Switching dynamics in ferroelectric thin films: An experimental survey

We have conducted a broad survey of switching behavior in thin films of a range of ferroelectric materials, including some materials that are not typically considered for FeRAM applications, and are hence less studied. The materials studied include: strontium bismuth tantalate (SBT), barium strontium titanate (BST), lead zicronate titanate (PZT), and potassium nitrate (KNO3). Switching in ferroelectric thin films is typically considered to occur by domain nucleation and growth. We discuss two models of frequency dependence of coercive field, the Ishisbashi-Orihara theory where the limiting step is domain growth and the model of Du and Chen where the limiting step is nucleation. While both models fit the data fairly well the temperature dependence of our results on PZT and BST suggest that the nucleation model of Du and Chen is more appropriate for the experimental results that we have obtained.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

Growth of SrS thin films by pulsed-laser deposition

High-quality luminescent thin films of strontium sulphide (SrS) with excellent stoichiometry have been grown by pulsed-laser deposition. The crystallinity, stoichiometry and cathodoluminescence (CL) have been investigated for the films deposited onto two differently coated glass substrates. Furthermore the importance of post-deposition annealing has been studied. SrS thin films grown at 450 degrees C onto glass substrates coated with tin-doped indium oxide show good crystallinity, with a preferred orientation along the (200) axis. Cerium-doped SrS (SrS:Ce) gives a strong blue CL output at 400 nm. Energy-dispersive X-ray spectroscopy shows that the films are stoichiometric and that the stoichiometry is controllable by varying deposition parameters.