生物－热催化过渡带沉积成岩演化及其成烃作用研究

The biothermocatalytic transitional zone gas is a new type of natural gas genetic theory, and also an clean, effective and high quality energy with shallow burial depth, wide distribution and few investment. Meanwhile, this puts biothermocatalytic transitional zone gas in important position to the energy resource and it is a challenging front study project. This paper introduces the concept, the present situation of study and developmental trend about biothermocatalytic transitional zone gas in detail. Then by using heat simulating of source rocks and catalysis mechanism analysis in the laboratory and studying structural evolution, sedimentation, diagenesis and the conditions of accumulation formation and so on, this paper also discusses catalytic mechanism and evolutionary model of the biothermocatalytic transitional zone gas formation, and establishes the methods of appraisal parameter and resources prediction about the biothermocatalytic transitional zone gas. At last, it shows that geochemical characteristics and differentiated mark of the biothermocatalytic transitional zone gas, and perfect natural gas genetic theory, and points out the conditions of accumulation formation, distribution characteristics and potential distribution region on the biothermocatalytic transitional zone gas m China. The paper mainly focuses on the formation mechanism and the resources potential about the biothermocatalytic transitional zone gas. Based on filed work, it is attached importance to a combination of macroscopic and microcosmic analysis, and the firsthand data are obtained to build up framework and model of the study by applying geologic theory. Based on sedimentary structure, it is expounded that structural actions have an effect on filling space and developmental cource of sediments and evolution of source rocks. Carried out sedimentary environment, sequence stratigraphy, sedimentary system and diagenesis and so on, it is concluded that diagenesis influences developmental evolution of source rocks, and basic geologic conditions of the biothermocatalytic transitional zone gas. Applying experiment simulating and catalytic simulating as well as chemical analysis, catalytic mechanism of clay minerals is discussed. Combined diagenecic dynamics with isotope fractionation dynamics, it is established that basis and method of resource appraisal about the biothermocatalytic transitional zone gas. All these results effectively assess and predict oil&gas resources about the biothermocatalytic transitional zone gas-bearing typical basin in China. I read more than 170 volumes on the biothermocatalytic transitional zone gas and complete the dissertation' summary with some 2.4 ten thousand words, draw up study contents in some detail and set up feasible experimental method and technologic course. 160 pieces of samples are obtained in oilfield such as Liaohe, Shengli, Dagang and Subei and so on, some 86 natural gas samples and more than 30 crude oil samples. Core profiles about 12 wells were observed and some 300 geologic photos were taken. Six papers were published in the center academic journal at home and abroad. Collected samples were analysised more than 1000 times, at last I complete this dissertation with more than 8 ten thousand words, and with 40 figures and 4 plates. According to these studies, it is concluded the following results and understandings. 1. The study indicates structural evolution and action of sedimentary basin influence and control the formation and accumulation the biothermocatalytic transitional zone gas. Then, the structural action can not only control accommodation space of sediments and the origin, migration and accumulation of hydrocarbon matters, but also can supply the origin of energy for hygrocarbon matters foramtion. 2. Sedimentary environments of the biothermocatalytic transitional zone gas are lake, river and swamp delta- alluvial fan sedimentary systems, having a warm, hot and humid climate. Fluctuation of lake level is from low to high., frequency, and piling rate of sedimentary center is high, which reflect a stable depression and rapidly filling sedimentary course, then resulting in source rocks with organic matter. 3. The paper perfects the natural gas genetic theory which is compound and continuous. It expounds the biothermocatalytic transitional zone gas is a special gas formation stage in continuous evolutionary sequence of organic matter, whose exogenic force is temperture and catalysis of clay minerals, at the same time, having decarbxylation, deamination and so on. 4. The methodology is established which is a combination of SEM, TEM and Engery spectrum analysis to identify microstructure of crystal morphology about clay minerals. Using differential thermal-chromatographic analysis, it can understand that hydrocarbon formation potential of different typies kerogens and catalytic method of all kinds of mineral matrix, and improve the surface acidity technology of clay minerals measured by the pyridine analytic method. 5. The experiments confirm catalysis of clay minerals to organic matter hygrocarbon formation. At low temperature (<300 ℃), there is mainly catalysis of montmorillonite, which can improve 2-3 times about produced gas of organic matters and the pyrolyzed temperature decreased 50 ℃; while at the high temperature, there is mainly catalysis of illite which can improve more than 2 times about produced gas of organic matters. 6. It is established the function relationship between organic matter (reactant) concentration and temperature, pressure, time, water and so on, that is C=f (D, t). Using Rali isotope fractionation effect to get methane isotope fractionation formula. According to the relationship between isotope fractionation of diagenesis and depth, and combined with sedimentary rate of the region, it is estimated that relict gas of the biothermocatalytic transitional zone gas in the representative basin. 7. It is revealed that hydrocarbon formation mechanism of the biothermocatalytic transitional zone gas is mainly from montmorillonite to mixed minerals during diagenesis. In interlayer, a lot of Al~(3+) substitute for Si~(4+), resulting in a imbalance between surface charge and interlayer charge of clay minerals and the occurrence of the Lewis and Bronsted acid sites, which promote to form the carbon cation. The cation can form alkene or small carbon cation. 8. It is addressed the comprehensive identification mark of the biothermo - catalytic transitional zone gas. In the temproal-spatial' distribution, its source rocks is mainly Palaeogene, secondly Cretaceous and Jurassic of Mesozoic, Triassic, having mudy rocks and coal-rich, their organic carbon being 0.2% and 0.4% respectively. The vitrinite reflection factor in source rocks Ro is 0.3-0.65%, a few up to 0.2%. The burial depth is 1000-3000m, being characterized by emerge of itself, reservoir of itself, shallow burial depth. In the transitional zone, from shallow to deep, contents of montmorillonites are progressively reduced while contents of illites increasing. Under SEM, it is observed that montmorillonites change into illite.s, firstly being mixed illite/ montmorillonite with burr-like, then itlite with silk-like. Carbon isotope of methane in the biothermocatatytic transitional zone gas , namely δ~(13)C_1-45‰- -60 ‰. 9. From the evolutionary sequence of time, distribution of the biothermocatalytic transitional zone gas is mainly oil&gas bearing basin in the Mesozoic-Neozoic Era. From the distribution region, it is mainly eastern stuctural active region and three large depressions in Bohaiwang basin. But most of them are located in evolutionary stage of the transitional zone, having the better relationship between produced, reservoir and seal layers, which is favorable about forming the biothermocatalytic transitional zone gas reservoir, and finding large gas (oil) field.

河流成因储层沉积微相与剩余油分布及形成机理研究

Based on the study of fluvial sandstone reservoir in upper of Guantao group in Gudao and Gudong oilfields, this paper first introduces A.D.Miall's(1996a) architectural-element analysis method that was summarized from ground outcrop scale into the reservoir formation research of the study area, more subtly divides sedimentary microfacies and establishes sedimentary model of research area.on this base, this paper summarizes the laws of residual oil distribution of fluvial formation and the control effect of sedimentary microfacies to residual oil distribution, and reveals residual oil formation mechanism. These results have been applied to residual oil production, and the economic effect is good. This paper will be useful for residual oil research and production and enhancement of oil recovery in similar reservoir. The major conclusions of this paper are as follows. 1. Using the architectural-element analysis method to the core data, a interfacial division scheme of the first to the dixth scale is established for the studied fluvial formation. 2.Seven architectural-elements are divided in upper of Guantao group of study area. The sandstone group 5～1+2 of Neogene upper Gutao group belongs to high sinuous fine grain meandering river, and the sandstone group 6 is sandy braided river. 3. Inter layer, the residual oil saturation of "non-main layer" is higher than "main layer", but the residual recoverable reserve of former is larger. Therefore, "main layer" is the main body of residual oil distribution. The upper and middle part of inner layer has lower permeability and strong seeping resistance. Addition to gravity effect in process of driving, its driving efficiency is low; residual oil saturation is high. Because of controlling of inside non-permeable interlayer or sedimentary construction, the residual oil saturation of non-driving or lower driving efficiency position also is high. On plane, the position of high residual oil saturation mostly is at element LV, CS, CH (FF), FF etc, Which has lower porosity and permeability, as well as lens sand-body and sand-body edge that is not controlled by well-net, non-perfect area of injection and production, lower press difference resort area of inter-well diffiuent-line and shelter from fault, local high position of small structure. 4.Microscopic residual oil mainly includes the non-moved oil in the structure of fine pore network, oil in fine pore and path, oil segment in pore and path vertical to flow direction, oil spot or oil film in big pore, residual oil in non-connective pore. 5.The most essential and internal controlling factor of fluvial formation residual oil distribution is sedimentary microfacies. Status of injection and production is the exterior controlling factor of residual oil distribution. 6. The controlling effect of formation sedimentary microfacies to residual oil distribution indicates inter-layer vertical sedimentary facies change in scale of injection and production layer-series, planar sedimentary face change and inner-layer vertical sedimentary rhythm and interbed in single layer to residual oil distribution. 7. It is difficult to clear up the inter-layer difference in scale of injection and production layer-series. The using status of minor layer is not good and its residual oil saturation is high relatively. It is obvious that inter-layer vertical sedimentary facies changes control inter-layer residual oil distribution at the same or similar conditions of injection and production. For fluvial formation, this vertical sedimentary facies change mainly is positive gyration. Namely, from down to top, channel sediment (element CHL, LA) changes into over-bank sediment (element LV, CR, CS). 8. In water-injection developing process of transverse connecting fluvial sandstone oil formation, injection water always comes into channel nearby, and breaks through along channel and orientation of high pressure gradient, does not expand into side of channel until pressure gradient of channel orientation changes into low. It brings about that water-driving status of over-bank sedimentary element formation (LV, CR, CS) is not good, residual oil saturation is high. In non-connective abandoned channel element (CH) formation with channel, because this reverse is difficult to control by injection and production well-series, its using status is not good, even terribly not good, residual oil is enrichment. 9. The rhythm and sedimentary structure, sedimentary facies change in single sand body brings about vertical changes of formation character, growth character of inner layer interbed. These are important factor of controlling and affecting vertical water spread volume and inner layer residual oil forming and distribution in single sand body. Positive rhythm, is the principal part of fluvial sandstone inner layer sedimentary rhythm. Namely, from down to upside, rock grain granularity changes from coarse to fine, seeping ability changes from strong to feebleness. It brings about that water-driving status of inner layer upside is not good, residual oil saturation is high. Inner layer interbed has different degree affecting and controlling effect to seeping of oil and water. Its affecting degree lies on interbed thickness, extending scale, position, and jeted segment of production or injection well. The effect of interbed at upside of oil formation to oil and water seeping is less; the effect of interbed at middle of oil formation to oil and water seeping is more. 10. Indoor experiment and research indicate that wettability, permeability step, vertical permeability, position of Kmax and ratio of oil viscousity and water viscousity all have great effect on the water-driving recovery ratio. 11. Microscopic residual oil distribution is affected and controlled by formation pore network structure, pressure field distribution, and oil characteristic. 12.The residual oil forming mechanism: the over-bank sedimentary element and upper part of a positive rhythm sandstone have fine pore and throat network, permeability is low, displacement pressure of pore and throat is high. The water-driving power usually falls short of displacement pressure that brings about injection water does not spread into these pore and throat network, thereby immovable oil area, namely residual oil, is formed. At underside of channel sedimentary element and positive rhythm sandstone, porosity and permeability is relatively high, connecting degree of pore and throat is high, displacement pressure of pore and throat is low. Thereby injection water is easy to enter into pore and throat, driving oil in them. Because the pore space is irregular, the surface of pore wall is coarse and non-flat. That the oil locate on concave hole of pore wall and the dead angle of pore, and the oil attaches on surface of pore wall by surface tension, are difficult to be peeled off, becoming water-driving residual oil (remaining oil). On the other hand, Because flowing section lessens, flowing resistance increase, action of capillary fore, or seeping speed decreases at process of transfer at pass narrow throat path in the course carried by driving water. The "oil drop", "oil bead", or "oil segment" peeled off by driving water is difficult to carry and to drive out by water at less pressure difference. Thereby they are enclosed in pore to form discontinuous residual oil. 13.This results described above have been applied in nine develop blocks of Gudao and Gudong oilfield. Its applying effect is marked through local injection production adjustment, deploying replacement well, repair hole, replacement envelop, block off water and profile control etc. Relative method and technology can be applied to other oil production area of Shengli oilfield, and obtain better economic and societal effect.

复杂断块油藏形成机制及剩余油预测

The central uplift in the Huimin depression is famous for its large amounts of faults and small-scale fault-block area, and it is the famed typical complicated fault-block group oil & gas field in the whole world. After many years of rolling exploration and exploitation, many complex oil &gas field have been discovered in the central uplift, and won the splendent fruit. With the gradual deepening and development of the rolling exploitation, the exploration faces more and more difficulties. Therefore, it is important to reveal the forming mechanism and distributing rule of the complex fault-block reservoir, and to realize the forecast of the complex fault-block reservoir, sequentially, expedite the exploration step. This article applies the new multi-subject theory, method and technique such as structure geometry, kinematics, dynamics, structural stress field, fluid potential field, well logging record and constrained inversion of seismic records, coherence analysis, the seal mold and seal history of oil-bounded fault etc, and try to reveal the forming mechanism and distributing law of the complex fault-block reservoir, in result, implements the forecast of the fault-block reservoir and the remaining oil distributing. In order to do so, this article synthetically carries out structural estimate, reservoir estimate, fault sealing history estimate, oil-bearing properties estimate and residual. This article also synthetically researches, describes and forecast the complex fault-block in Huimin depression by use of the techniques, e.g. seismetic data post-stack processing technique, multi-component demarcating technique, elaborate description technique for the fault-block structure, technique of layer forecasting, fault sealing analysis technique, comprehensive estimate technique of fault-block, comprehensive analysis and estimate technique of remaining oil etc. The activities of the faults varies dramatically in the Huimin depression, and most of the second-class and the third-class faults are contemporaneous faults, which control the macroscopical distribution of the reservoir in the Huimin depression. The fourth-class faults cause the complication between the oil & gas among the fault-blocks. The multi-period strong activities of the Linyi fracture resulted in the vertical migration of large amount of oil & gas along with the faults. This is the main reason for the long vertical distribution properties near the Linyi fracture in the Huimin depression. The sealing ability of the fault is controlled by the property,size and direction of the main stress, the contact relationship of the both sides of the fault, the shale polluting factor, and the configuration relationship between the fault move period and the migration period of oil & gas. The article suggest four fault-sealing modes in the research zone for the first time, which establishes the foundation for the further forecast of the complex fault-block reservoir. Numerical simulation of the structural stress field reveals the distribution law and the evolvement progress of the three-period stress field from the end of the Dongying period to the Guantao period to nowadays. This article puts forward that the Linyi and Shanghe regions are the low value of the maximum main stress data. This is combined with the fault sealing history estimate, then multi-forming-reservoir in the central uplift is put forward. In the Shanghe oilfield, the article establishes six reservoir geological modes and three remaining oil distributing modes(the plane, the inside layer and the interlayer), then puts forward six increase production measure to enhance the remaining oil recovery ratio. Inducting the exploitation of oilfield, it wins notable economic effects and social effects.

河流-三角洲储层剩余油分布模式及预测

Aim at the variousness and complexity of the spatial distribution of Remaining Oil in the fluvial and delta facies reservoir in paper. For example, in the La-Sa-Xing oilfield of Daqing, based on the research of the control factor and formation mechanization of block, single layer, interlayer and micromechanism, synthesizing the theories and methods of geology, well logging, reservoir engineering, artificial intelligence, physical simulation test , and computer multidisciplinary; Fully utilizing the material of geology, well logging, core well, dynamic monitor of oil and water well, and experimental analysis, from macro to micro, from quality to quantity, from indoor to workplace, we predicted the potentiality and distribution according to the four levels of Block, single layer, interlayer and micromechanism, and comprehensively summarized the different distribution pattern of remaining oil in the fluvial and delta facies reservoir This paper puts forward an efficient method to predict the remaining recoverable reserves by using the water flooding characteristic curve differential method and neutral network; for the first time utilizes multilevel fuzzy comprehensive judgment method and expert neutral network technology to predict the remaining oil distribution in the single layer? comprehensively takes advantage of reservoir flowing unit, indoor physical simulation test, inspection well core analysis and well-logging watered-out layer interpretation to efficiently predict the distribution of remaining oil; makes use of core analysis of different periods and indoor water driving oil test to study the micro distribution of remaining oil and the parameters varying law of reservoir substance properties, rock properties, wetting properties. Based on above, the remaining oil distribution predicting software is developed, which contains four levels of block, single layer, interlayer and micromechanism. This achievement has been used inLa-Sa-Xing oil field of Daqing and good results have been received.

高含水油藏复合驱剩油分布研究-以羊三木油田馆陶组油藏复合驱为例

Based on the study of the combined flooding test block of Guantao formation in Third faulted block of Yangsanmu oil field, this paper carries out the integration of reservoir precise characterization for very high water cut reservoir, establishes precise 3D geologic model for high water cut development period and states the changing law of the reservoir architecture dtiring development by combined flooding. Then, by subdivided the thick oil reservoir, the study of remaining oil saturation monitoring in fiber glass cased well and tracer monitoring is developed. According the study of multiple constrained combined flooding reservoir numerical simulation, remaining oil distribution are predicted, the methods architecture of predicting remaining oil distribution are established for fluvial facies reservoir at late development stage, develops plan is designed and adjustment associating technologies for enhancing oil recovery. On these base, related measures for tapping the potential are given, it is verified and optimized through the field former test and the good economic effect is achieved . The major achievements of this paper are as follows. The changing law of the reservoir architecture and it's property parameters is revealed, The result indicates that the temperature-pressure of the injecting material and the interaction effect of the injecting material and reservoir petrography are the main factors of the dynamic changes of the reservoir architecture. The quantitative reservoir geologic model, which is tallied with dynamic reservoir parameters of the study area, is established. Subdivided the thick oil reservoir is very important for the study of the remaining oil distribution within the thick oil reservoir. Subdivided the thick oil reservoir technology, which consists of six technologies as follow: micro-cyclic divided, flow unit method, architectural element method, high resolution log technology, high resolution-process technology for normal logging data and using the production data is presented. 3. It is established dynamic monitoring system of remaining oil saturation quantitative research which are inner and interlayer remaining oil saturation from time-lapse logging in fiber glass cased well, inter-well remaining oil saturation from the technology of isotopic tracer monitoring technology, and 4d remaining oil saturation distribution from combined flooding numerical modeling integrated by production datao The forming mechanism of remaining oil for polymer flooding and alkali/polymer combined flooding is clarified, and the plane and vertical distribution law of remaining oil after combined flooding is revealed. Predicting methods and technologies for the combined flooding reservoir of fluvial facies is developed. Combined flooding has been achieved good displacement result in the pilot of Third fault block in Yangsanmu oil field, and accumulated types of important parameters and optimum plans, this technology of combined flooding is expected to increase recovery ratio by 4.77%.

板北断块油藏储层均质特征与剩余油分布研究

With the growing development and perfection of reservoir describing technology, its research achievements have played an increasingly important role in old oilfields in recent years. Reservoir description quantitatively describes, characterizes and predicts every kind of reservoir characters in 3D space. The paper takes Banbei block reservoir as an object, studies the reservoir characters and residual oil distributing characteristics of gravity flow genetic reservoir, and definitudes potential adjustment direction of reservoir development. Main achievements are gained as follows. Through fine correlation of strati graphic sequence, the classification of layers and single sands of main payzones in Banbei block is ascertained, the classifying methods of sedimentary unit in gravity flow reservoir characterized with picked cyclical marker bed are formed. On the basis of comprehensive logging evaluation, depositional characters of Banbei block are studied, and classifying methods of sedimentary microfacies in gravity flow reservoir are described. The sedimentary background of main oil layers in Banbei block is open lake with shallow water, and belongs to lacustrine underwater gravity flow- lacustrine phase depositional system. Main microfacies types are underwater water course^ water course side-wing, underwater floodplain, between two water courses, and lacustrine mud, etc. Reservoir sands mainly are underwater water course sands. Influenced by distributing characters of gravity flow underwater water course, sand shapes in plane mainly are stripe, finger-shape, tongue-shape. Sand distribution shows obvious split property. Sands overlap each other. According to comprehensive analysis of lithologic data, logging parameters, and dynamic production data, the researching threads and methods of reservoir heterogeneous characters are perfected. The depositional characters of gravity flow underwater water course in Banbei block determine its high reservoir heterogeneity. Macroscopic heterogeneity is studied in many aspects such as the scale of layers, the scale of single sands, in-situ scale, the distribution of interlayer types, the interlayer scale, and heterogeneity in plane. Thus, heterogeneous characters of reservoir are thoroughly analyzed. Through microscopic research of reservoir, the types of porous structure and related parameters are determined. According to the analysis of dynamic production data, the reaction and inner influential factors of reservoir heterogeneity in waterflood development are further revealed. Started with the concept and classifying methods of flow unit, clustering classification which can better meet the requirements of production is formed. The flow unit of Banbei block can be classified into four types. According to comprehensive evaluation, the first and second type of flow unit have better percolating capability and reserving capability. Research thread of 3D model-building and reservoir numerical simulation combined as an integral is adopted. The types and characters of residual oil distribution are determined. Residual oil of Banbei block mainly distributes in the boundary of sands, near the faults, areas with non-perfect injection-production well pattern , undeveloped sands, vertically poor developed layers. On the basis of comprehensive reservoir study, the threads and methods of improving development effect towards reservoir with high water cut, high recovery percent, serious heterogeneity are ascertained. The whole waterflood development effect of Banbei block reservoir is good. Although its water cut and recovery percent is relatively high, there is still some potential to develop. According to depositional characters of gravity flow and actual production situation? effective means of further improving development level are as follows. We should drill new wells in every kind of areas abounding with residual oil, implement comprehensive measures such as increasing liquid discharge, cyclic waterflood, changing fluid direction when injection-production well pattern is perfected, improve water quality, enhance displacement efficiency in flooding.

大港油田孔南地区孔一段储层流动单元研究

The main reservoir type in the south of Dagang Oilfield is alluvial reservoir. In this paper, the reservoir structure model and the distribution of connected body and flow barrier were built on base of the study of high-resolution sequential stratigraphic skeleton and fine sedimentary microfacies on level of single sandbody. Utilizing the static and dynamic data synthetically and carrying out the comparision of the classification method for reservoir flow unit in different reservoir, the criterion, which can be used to classify the flow unit in first section of Kongdian formation of Kongnan area, was defined. The qualitative method of well-to-well correlation and the quantitative method of conditional simulation using multiple data are adopted to disclose the oil and water moving regulation in different flow unit and the distribution rule of remaining oil by physical simulation measure. A set of flow unit study method was formed that is suit for the Dagang Oilfield on account of the remaining oil production according to the flow unit. Several outstanding progresses was obtained in the following aspects:It is considered that the reservoir structure of Zao V iow oil group- Zao Vup4 layerand are jigsaw-puzzled reservoir, while ZaoVup3-ZaoVupi layers are labyrinth reservoir,which are studied on base of high-resolution sequential stratigraphic skeleton on the levelof single sandbody in first section of Kongdian formation of Kongnan area and accordingto the study of fine sedimentary microfacies and fault sealeing.When classifying the flow unit, only permeability is the basic parameter using thestatic and dynamic data and, and also different parameters should be chose or deleted, suchas porosity, effective thickness, fluid viscosity and so on, because of the weak or stronginterlayer heterogeneous and the difference of interlayer crude oil character.The method of building predicting-model of flow unit was proposed. This methodis according to the theories of reservoir sedimentology and high-resolution sequencestratigraphic and adopts the quantitative method of well-to well correlation and the quantitative method of stochastic simulation using integrateddense well data. Finally the 3-D predicting-model of flow unit and the interlay er distribution model in flow unit were built which are for alluvial fan and fan delta fades in first section of Kongdian formation of Kongnan area, and nine genetic model of flow unit of alluvial environment that spread in the space were proposed.(4) Difference of reservoir microscopic pore configuration in various flow units and difference of flow capability and oil displacement effect were demonstrated through the physical experiments such as nuclear magnetic resonance (NMR), constant rate mercury penetration, flow simulation and so on. The distribution of remaining oil in this area was predicted combining the dynamic data and numerical modeling based on the flow unit. Remaining oil production measure was brought up by the clue of flow unit during the medium and late course of the oilfield development.

单（多）井抽灌对浅部地温场的影响研究

The technique of energy extraction using groundwater source heat pumps, as a sustainable way of low-grade thermal energy utilization, has widely been used since mid-1990's. Based on the basic theories of groundwater flow and heat transfer and by employing two analytic models, the relationship of the thermal breakthrough time for a production well with the effect factors involved is analyzed and the impact of heat transfer by means of conduction and convection, under different groundwater velocity conditions, on geo-temperature field is discussed.A mathematical model, coupling the equations for groundwater flow with those for heat transfer, was developed. The impact of energy mining using a single well system of supplying and returning water on geo-temperature field under different hydrogeological conditions, well structures, withdraw-and-reinjection rates, and natural groundwater flow velocities was quantitatively simulated using the finite difference simulator HST3D. Theoretical analyses of the simulated results were also made. The simulated results of the single well system indicate that neither the permeability nor the porosity of a homogeneous aquifer has significant effect on the temperature of the production segment provided that the production and injection capability of each well in the aquifers involved can meet the designed value. If there exists a lower permeable interlayer, compared with the main aquifer, between the production and injection segments, the temperature changes of the production segment will decrease. The thicker the interlayer and the lower the interlayer permeability, the longer the thermal breakthrough time of the production segment and the smaller the temperature changes of the production segment. According to the above modeling, it can also be found that with the increase of the aquifer thickness, the distance between the production and injection screens, and/or the regional groundwater flow velocity, and/or the decrease of the production-and-reinjection rate, the temperature changes of the production segment decline. For an aquifer of a constant thickness, continuously increase the screen lengths of production and injection segments may lead to the decrease of the distance between the production and injection screens, and the temperature changes of the production segment will increase, consequently.According to the simulation results of the single well system, the parameters, that can cause significant influence on heat transfer as well as geo-temperature field, were chosen for doublet system simulation. It is indicated that the temperature changes of the pumping well will decrease as the aquifer thickness, the distance between the well pair and/or the screen lengths of the doublet increase. In the case of a low permeable interlayer embedding in the main aquifer, if the screens of the pumping and the injection wells are installed respectively below and above the interlayer, the temperature changes of the pumping well will be smaller than that without the interlay. The lower the permeability of the interlayer, the smaller the temperature changes. The simulation results also indicate that the lower the pumping-and-reinjection rate, the greater the temperature changes of the pumping well. It can also be found that if the producer and the injector are chosen reasonably, the temperature changes of the pumping well will decline as the regional groundwater flow velocity increases. Compared with the case that the groundwater flow direction is perpendicular to the well pair, if the regional flow is directed from the pumping well to the injection well, the temperature changes of the pumping well is relatively smaller.Based on the above simulation study, a case history was conducted using the data from an operating system in Beijing. By means of the conceptual model and the mathematical model, a 3-D simulation model was developed and the hydrogeological parameters and the thermal properties were calibrated. The calibrated model was used to predict the evolution of the geo-temperature field for the next five years. The simulation results indicate that the calibrated model can represent the hydrogeological conditions and the nature of the aquifers. It can also be found that the temperature fronts in high permeable aquifers move very fast and the radiuses of temperature influence are large. Comparatively, the temperature changes in clay layers are smaller and there is an obvious lag of the temperature changes. According to the current energy mining load, the temperature of the pumping wells will increase by 0.7°C at the end of the next five years. The above case study may provide reliable base for the scientific management of the operating system studied.

Modification of GaAs Schottky diodes by thin organic interlayers

Modification of GaAs Schottky diodes by thin organic interlayers, A.R. Vearey-Roberts and D.A. Evans, Appl. Phys. Lett. 86, 072105 (2005)

Nano-urchin: The formation and structure of high-density spherical clusters of vanadium oxide nanotubes

We report the observation of urchin-like nanostructures consisting of high-density spherical nanotube radial arrays of vanadium oxide nanocomposite, successfully synthesized by a simple chemical route using an ethanolic solution of vanadium tri-isopropoxide and alkyl amine hexadecylamine for 7 days at 180oC. The results show that the growth process of the NanoUrchin occurs in stages, starting with a radial self-organized arrangement of lamina followed by the rolling of the lamina into nanotubes. The longest nanotubes are measured to be several micrometers in length with diameters of ~120 nm and hollow centers typically measured to be ~75 nm. The NanoUrchin have an estimated density of nanotubes of ~40 sr-1. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. The interlayer distance is measured to be 2.9 ± 0.1 nm and electron diffraction identified the vanadate phase in the VOx nanocomposite as orthorhombic V2O5. These nanostructures may be used as three-dimensional composite materials and as supports for other materials.

Accommodating curvature in a highly ordered functionalized metal oxide nanofiber: synthesis, characterization and multi-scale modeling of layered nanosheets

A key element in the rational design of hybrid organic-inorganic nanostructures, is control of surfactant packing and adsorption onto the inorganic phase in crystal growth and assembly. In layered single crystal nanofibers and bilayered 2D nanosheets of vanadium oxide, we show how the chemisorption of preferred densities of surfactant molecules can direct formation of ordered, curved layers. The atom-scale features of the structures are described using molecular dynamics simulations that quantify surfactant packing effects and confirm the preference for a density of 5 dodecanethiol molecules per 8 vanadium attachment sites in the synthesised structures. This assembly maintains a remarkably well ordered interlayer spacing, even when curved. The assemblies of interdigitated organic bilayers on V2O5 are shown to be sufficiently flexible to tolerate curvature while maintaining a constant interlayer distance without rupture, delamination or cleavage. The accommodation of curvature and invariant structural integrity points to a beneficial role for oxide-directed organic film packing effects in layered architectures such as stacked nanofibers and hybrid 2D nanosheet systems.

Atomic layer deposition of copper for CMOS interconnects

This work concerns the atomic layer deposition (ALD) of copper. ALD is a technique that allows conformal coating of difficult topographies such as narrow trenches and holes or even shadowed regions. However, the deposition of pure metals has so far been less successful than the deposition of oxides except for a few exceptions. Challenges include difficulties associated with the reduction of the metal centre of the precursor at reasonable temperatures and the tendency of metals to agglomerate during the growth process. Cu is a metal of special technical interest as it is widely used for interconnects on CMOS devices. These interconnects are usually fabricated by electroplating, which requires the deposition of thin Cu seed layers onto the trenches and vias. Here, ALD is regarded as potential candidate for replacing the current PVD technique, which is expected to reach its limitations as the critical dimensions continue to shrink. This work is separated into two parts. In the first part, a laboratory-scale ALD reactor was constructed and used for the thermal ALD of Cu. In the second part, the potentials of the application of Cu ALD on industry scale fabrication were examined in a joint project with Applied Materials and Intel. Within this project precursors developed by industrial partners were evaluated on a 300 mm Applied Materials metal-ALD chamber modified with a direct RF-plasma source. A feature that makes ALD a popular technique among researchers is the possibility to produce high- level thin film coatings for micro-electronics and nano-technology with relatively simple laboratory- scale reactors. The advanced materials and surfaces group (AMSG) at Tyndall National Institute operates a range of home-built ALD reactors. In order to carry out Cu ALD experiments, modifications to the normal reactor design had to be made. For example a carrier gas mechanism was necessary to facilitate the transport of the low-volatile Cu precursors. Precursors evaluated included the readily available Cu(II)-diketonates Cu-bis(acetylacetonate), Cu-bis(2,2,6,6-tetramethyl-hepta-3,5-dionate) and Cu-bis(1,1,1,5,5,5-hexafluoacetylacetonate) as well as the Cu-ketoiminate Cu-bis(4N-ethylamino- pent-3-en-2-onate), which is also known under the trade name AbaCus (Air Liquide), and the Cu(I)- silylamide 1,3-diisopropyl-imidazolin-2-ylidene Cu(I) hexamethyldisilazide ([NHC]Cu(hmds)), which was developed at Carleton University Ottawa. Forming gas (10 % H2 in Ar) was used as reducing agent except in early experiments where formalin was used. With all precursors an extreme surface selectivity of the deposition process was observed and significant growth was only achieved on platinum-group metals. Improvements in the Cu deposition process were obtained with [NHC]Cu(hmds) compared with the Cu(II) complexes. A possible reason is the reduced oxidation state of the metal centre. Continuous Cu films were obtained on Pd and indications for saturated growth with a rate of about 0.4 Å/cycle were found for deposition at 220 °C. Deposits obtained on Ru consisted of separated islands. Although no continuous films could be obtained in this work the relatively high density of Cu islands obtained was a clear improvement as compared to the deposits grown with Cu(II) complexes. When ultra-thin Pd films were used as substrates, island growth was also observed. A likely reason for this extreme difference to the Cu films obtained on thicker Pd films is the lack of stress compensation within the thin films. The most likely source of stress compensation in the thicker Pd films is the formation of a graded interlayer between Pd and Cu by inter-diffusion. To obtain continuous Cu films on more materials, reduction of the growth temperature was required. This was achieved in the plasma assisted ALD experiments discussed in the second part of this work. The precursors evaluated included the AbaCus compound and CTA-1, an aliphatic Cu-bis(aminoalkoxide), which was supplied by Adeka Corp.. Depositions could be carried out at very low temperatures (60 °C Abacus, 30 °C CTA-1). Metallic Cu could be obtained on all substrate materials investigated, but the shape of the deposits varied significantly between the substrate materials. On most materials (Si, TaN, Al2O3, CDO) Cu grew in isolated nearly spherical islands even at temperatures as low as 30 °C. It was observed that the reason for the island formation is the coalescence of the initial islands to larger, spherical islands instead of forming a continuous film. On the other hand, the formation of nearly two-dimensional islands was observed on Ru. These islands grew together forming a conductive film after a reasonably small number of cycles. The resulting Cu films were of excellent crystal quality and had good electrical properties; e.g. a resistivity of 2.39 µΩ cm was measured for a 47 nm thick film. Moreover, conformal coating of narrow trenches (1 µm deep 100/1 aspect ratio) was demonstrated showing the feasibility of the ALD process.

Atomic layer deposition of interface control layers for the fabrication of III/V MOS devices

The continued advancement of metal oxide semiconductor field effect transistor (MOSFET) technology has shifted the focus from Si/SiO2 transistors towards high-κ/III-V transistors for high performance, faster devices. This has been necessary due to the limitations associated with the scaling of the SiO2 thickness below ~1 nm and the associated increased leakage current due to direct electron tunnelling through the gate oxide. The use of these materials exhibiting lower effective charge carrier mass in conjunction with the use of a high-κ gate oxide allows for the continuation of device scaling and increases in the associated MOSFET device performance. The high-κ/III-V interface is a critical challenge to the integration of high-κ dielectrics on III-V channels. The interfacial chemistry of the high-κ/III-V system is more complex than Si, due to the nature of the multitude of potential native oxide chemistries at the surface with the resultant interfacial layer showing poor electrical insulating properties when high-κ dielectrics are deposited directly on these oxides. It is necessary to ensure that a good quality interface is formed in order to reduce leakage and interface state defect density to maximise channel mobility and reduce variability and power dissipation. In this work, the ALD growth of aluminium oxide (Al2O3) and hafnium oxide (HfO2) after various surface pre-treatments was carried out, with the aim of improving the high-κ/III-V interface by reducing the Dit – the density of interface defects caused by imperfections such as dangling bonds, dimers and other unsatisfied bonds at the interfaces of materials. A brief investigation was performed into the structural and electrical properties of Al2O3 films deposited on In0.53Ga0.47As at 200 and 300oC via a novel amidinate precursor. Samples were determined to experience a severe nucleation delay when deposited directly on native oxides, leading to diminished functionality as a gate insulator due to largely reduced growth per cycle. Aluminium oxide MOS capacitors were prepared by ALD and the electrical characteristics of GaAs, In0.53Ga0.47As and InP capacitors which had been exposed to pre-pulse treatments from triethyl gallium and trimethyl indium were examined, to determine if self-cleaning reactions similar to those of trimethyl aluminium occur for other alkyl precursors. An improved C-V characteristic was observed for GaAs devices indicating an improved interface possibly indicating an improvement of the surface upon pre-pulsing with TEG, conversely degraded electrical characteristics observed for In0.53Ga0.47As and InP MOS devices after pre-treatment with triethyl gallium and trimethyl indium respectively. The electrical characteristics of Al2O3/In0.53Ga0.47As MOS capacitors after in-situ H2/Ar plasma treatment or in-situ ammonium sulphide passivation were investigated and estimates of interface Dit calculated. The use of plasma reduced the amount of interface defects as evidenced in the improved C-V characteristics. Samples treated with ammonium sulphide in the ALD chamber were found to display no significant improvement of the high-κ/III-V interface. HfO2 MOS capacitors were fabricated using two different precursors comparing the industry standard hafnium chloride process with deposition from amide precursors incorporating a ~1nm interface control layer of aluminium oxide and the structural and electrical properties investigated. Capacitors furnished from the chloride process exhibited lower hysteresis and improved C-V characteristics as compared to that of hafnium dioxide grown from an amide precursor, an indication that no etching of the film takes place using the chloride precursor in conjunction with a 1nm interlayer. Optimisation of the amide process was carried out and scaled samples electrically characterised in order to determine if reduced bilayer structures display improved electrical characteristics. Samples were determined to exhibit good electrical characteristics with a low midgap Dit indicative of an unpinned Fermi level

Properties of InAlN/GaN Heterostructures Prepared by Molecular Beam Epitaxy

InAlN thin films and InAlN/GaN heterostructures have been intensively studied over recent years due to their applications in a variety of devices, including high electron mobility transistors (HEMTs). However, the quality of InAlN remains relatively poor with basic material and structural characteristics remain unclear.

Molecular beam epitaxy (MBE) is used to synthesize the materials for this research, as MBE is a widely used tool for semiconductor growth but has rarely been explored for InAlN growth. X-ray photoelectron spectroscopy (XPS) is used to determine the electronic and chemical characteristics of InAlN surfaces. This tool is used for the first time in application to MBE-grown InAlN and heterostructures for the characterization of surface oxides, the bare surface barrier height (BSBH), and valence band offsets (VBOs).

The surface properties of InAlN are studied in relation to surface oxide characteristics and formation. First, the native oxide compositions are studied. Then, methods enabling the effective removal of the native oxides are found. Finally, annealing is explored for the reliable growth of surface thermal oxides.

The bulk properties of InAlN films are studied. The unintentional compositional grading in InAlN during MBE growth is discovered and found to be affected by strain and relaxation. The optical characterization of InAlN using spectroscopy ellipsometry (SE) is also developed and reveals that a two-phase InAlN model applies to MBE-grown InAlN due to its natural formation of a nanocolumnar microstructure. The insertion of an AlN interlayer is found to mitigate the formation of this microstructure and increases mobility of whole structure by fivefold.

Finally, the synthesis and characterization of InAlN/GaN HEMT device structures are explored. The density and energy distribution of surface states are studied with relationships to surface chemical composition and surface oxide. The determination of the VBOs of InAlN/GaN structures with different In compositions are discussed at last.

Ag+- and Zn2+-exchange kinetics and antimicrobial properties of 11 angstrom tobermorites

Ag+- and Zn2+-exchanged zeolites zeolites and clays have been used as coatings and in composites to confer broad-spectrum antimicrobial properties on a range of technical and biomedical materials. 11 angstrom tobermorite is a bioactive layer lattice ion exchanger whose potential as a carrier for Ag+ and Zn2+ ions in antimicrobial formulations has not yet been explored. In view of this, batch Ag+- and Zn2+-exchange kinetics of two structurally distinct synthetic 11 angstrom tobermorites and their subsequent bactericidal action against Staphylococcus aureus and Pseudomonas aeruginosa are reported. During the exchange reactions, Ag+ ions were found to replace labile interlayer cations; whereas, Zn2+ ions also displaced structural Ca2+ ions from the tobermorite lattice. In spite of these different mechanisms, a simple pseudo-second-order model provided a suitable description of both exchange processes (R-2 >= 0.996). The Ag+- and Zn2+-exchanged tobermorite phases exhibited marked bacteriostatic effects against both bacteria, and accordingly, their potential for use as antimicrobial materials for in situ bone tissue regeneration is discussed. (C) 2008 Elsevier Ltd. All rights reserved.