【作者】 李征；

【导师】 魏雨；

【作者基本信息】 河北师范大学 ， 物理化学， 2006， 硕士

【摘要】 透明导电氧化物薄膜自1907年首次制备成功后,已经在生产、生活的各个方面得到了广泛的应用。由于目前应用较广泛的氧化铟锡（ITO）导电薄膜生产成本较高,稳定性不够,所以掺铝氧化锌导电薄膜已经成为其最好的替代品。氧化锌铝（ZAO）虽然具有良好的导电性能,但生产工艺还是比较复杂。因此,能否找到简便、易控制的方法来合成铝掺杂的氧化锌导电陶瓷靶材,是低成本生产导电薄膜的关键。 本论文采用了液相方法:沸腾回流法和共沉淀法来制备ZAO粉体。这两种方法都具有工艺流程简单,条件温和,易控制等优点。我们的主要工作及成果详述如下: 第一,分别选取Zn（NO₃）₂和Al（NO₃）₃体系、Zn（CH₃COO）₂和Al（NO₃）₃体系及ZnSO₄和Al₂（SO₄）₃体系作为前驱体,采用沸腾回流法成功制备了一系列不同铝掺杂量的ZAO粉体,并且通过实验总结出了最终产物中铝元素的含量随前驱体中铝盐与锌盐浓度比变化的规律,从而能够人为控制ZAO粉体中铝元素的含量。研究了不同掺杂量ZAO粉体的形貌、结构和电学性质。用SEM观察了ZAO粉体的形貌,分析了不同形貌的成因,发现硝酸盐为前驱体时样品的形貌是随掺杂量的增大从棒状变化为准球形,而以醋酸盐为前驱体则是从哑铃形随掺杂量的增大变成细小的颗粒状,发现不同形貌的形成与反应体系中阴离子的作用有关。通过改变反应物的pH值、前驱体煅烧温度及掺杂量测定了样品的方块电阻值,发现方块电阻随pH值的增大而增大,随着煅烧温度先减小后增大,随着掺杂量先减小后增大。根据得到的结论确定沸腾回流法制备ZAO粉体前驱体pH值应控制为弱碱性,煅烧温度500℃～600℃较好,最佳掺杂量硝酸盐为4.67%,硝酸盐制备的样品比醋酸盐制备的样品导电性能要好。 第二,分别选取Zn（NO₃）₂和Al（NO₃）₃体系及ZnSO₄和Al₂（SO₄）₃体系作为前驱体,采用共沉淀法制备出了一系列掺杂量不同的ZkO粉体,并且总结出产物中铝元素的变化规律,并且发现在前驱体相同且锌盐和铝盐浓度比相同的情况下,两种方法比较,共沉淀法的掺杂效果更好。对该种方法制备的产品的形貌、结构、电学性质进行研究发现,由于反应中我们加入了另外一种沉淀剂NH₄HCO₃,沉淀剂更多还原

【Abstract】 The transparent electric conduction oxide compound thin films prepared for the first time since 1907 successfully,Already in the production, life each aspect obtained the widespread application. Because at present applies the widespread Sn-doped In₂O₃（ITO） electric conduction thin films production cost high, the stability is insufficient, therefore Al-doped ZnO electric conduction thin films already to become its best substitute. Al-doped ZnO （ZAO） although has the good electric conductivity, but the production craft quite is complex, realizes the industrialization production with difficulty. Therefore, whether found the method which simple, is easy to control to synthesize the Al-doped ZnO electric conduction ceramics target material, is the mass production Al-doped ZnO electric conduction thin film substitution at present the commonly used Sn-doped In₂O₃ electric conduction thin film key.Based on the present ZAO industrialization production present situation, the present paper used liquid phase method: The boiling reflux and the co-precipitation law prepares the ZAO powder . These two methods all have the technical process simply, condition temperate, is easy to control and so on the merit. Our main work and the achievement relate in detail as follows:First, separately selects Zn （NO3） 2andAl （N03） 3 systems, Zn （CH3COO） 2 and Al （NO3） 3 systems, ZnS04and Al2 （S04） 3 systems took the forerunner body, used the boiling reflux to success to prepare a series of dopings quantity different ZAO powder , and summarized in the end product through the repeated test the aluminum element content along with the forerunner body in the aluminum salt and the zinc salt density compared to the change rule, thus could in the very good control ZAO powder body the aluminum element content. We the sample which resulted in to the system have carried on the attribute, studied the different doping to measure the ZAO powder the appearance, the structure, the electricity nature. Through the change sample pH value, the calcining heat and the doping quantity observe the sample the block resistance value, obtains the conclusion: The block resistance increases along with the pH value but increases, reduces first after the calcining heat increases, reduces first after the doping quantity increases. According to the conclusion which obtains determined the boiling reflux prepares ZAO the powder forerunner body pH value to be supposed to control is the weak basicity, the calcining heat 500 °C 600 °C is better, best dopes the quantity nitrate is 4.67%, the nitrate preparation sample is friends with compared to the acetate preparation sample electric conductivity. The nitrate for the forerunner body fashion appearance is along with doping quantity increasing from the clavate change to theirregular accurate sphere, but take acetate as forerunner body then is dumbbell-shaped increases from the pure zinc oxide along with the doping quantity turns tiny granulated.Second, selects Zn （NO3） 2 and Al （NO3） 3 systems, ZnSO4 and Al2 （SO4） 3 systems took the forerunner body, used altogether the precipitation method to prepare a series of dopings quantity different ZAO powder , and summarized in the end product through the repeated test which prepared with this method the aluminum element content along with the forerunner body in the aluminum salt and the zinc salt density compared to the change rule, and discovered in forerunner body same also zinc salt and aluminum salinity compared to same situation in, two methods compared, the co-precipitation method doping effect was better. To this method preparation product appearance, the structure, the electricity nature carry on the research discovery, because responded we have joined other one kind of precipitating agent NH4HCO3.The precipitating agent density increased have been very many, the fineness ratio same system boiling reflux preparation sample reduced its grain after obviously to reduce greatly generally between 20 30nm, the appearance presented a more regular sphere, obtained the grain after for the nanometer level powder body, reducing which the grain passed through had the vital significance to the ZAO optical quality improvement.Third, we have conducted the optical quality research to two methods preparations sample, we determined the sample UV spectrum, the fluorescence spectrum separately, the findings had indicated, mixed Al in ZnO, was advantageous in the zinc oxide ultraviolet absorption, also along with doping quantity increasing, the absorption strength also increased along with it. Two kind of sides legal systems result in the ZAO fluorescence absorption band differs from, altogether precipitation method preparation sample granularity quite small, the fluorescence absorption band quite is obvious, the boiling reflux preparation sample granularity in a micron level, absorbs is not very obvious.Through massive experiments us to draw the conclusion, the fluid physiognomy may realize the aluminum element doping, and may in the accurate control product the aluminum element doping quantity, the method which uses compared to the predecessor simpler, also is easier to control, has provided the certain theory basis for the industrialization production. Through to the product attribute and the research, proved two methods preparations the product all has the good performance, co-precipitation preparation sample grain after in a nanometer level, besides has the better electricity nature.更多还原