锰酸锶镧薄膜的复合溶胶—凝胶法制备工艺研究
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摘要
稀土钙钛矿结构材料LaMO_3(M=Cr、Fe、Mn等)具有明显的负温度系数(NTC)特征,可以作为负温度系数热敏电阻的新一代基础材料。通过掺杂等手段可以对LaMO_3材料的电阻-温度关系进行控制,使其获得最佳的阻-温性能。若将此类材料涂覆在适宜的基底上,结合其优异的高温性能与电阻温度特性,有望作为新一代薄膜热敏材料开发出耐酸、碱和腐蚀性气体的直接接触式实用温度传感器。
本研究的目的是在Al_2O_3基底上制备组织致密、且有一定厚度的La_(1-x)Sr_xMO_3薄膜,进而探讨此类薄膜的电性能。研究主要集中在:采用复合溶胶-凝胶方法制备La_(1-x)Sr_xMnO_3薄膜,用XRD、SEM等手段对不同薄膜的结构、相组成、表面和截面组织形貌进行分析,研究各工艺参数(包括前驱体溶液浓度、掺杂量、粉体加入量、封孔致密化、浸渍次数、预烧温度和烧结温度等)与薄膜组织的关系;研究La_(1-x)Sr_xMnO_3薄膜的电性能,找出决定电性能的关键工艺参数;探讨LaMO_3薄膜的形成机制、钙钛矿结构的掺杂导电机理等相关问题。
通过系统地对比研究,优选出了在Al_2O_3基底上制备高质量La_(1-x)Sr_xMO_3薄膜的复合溶胶-凝胶制备工艺,该工艺的关键为:首先制备掺锶锰酸镧纳米粉体和同组分的锰酸锶镧溶胶;然后将纳米粉体和溶胶按一定比例配合,制成复合浆料;最后采用浸渍提拉法在经预处理的基底上进行涂覆并煅烧成膜。在复合溶胶-凝胶制备工艺中,影响薄膜质量的主要因素为:粉体加入量、分散剂、浸渍次数、封孔工艺、热处理温度等。
XRD和SEM表征结果证明,用复合溶胶-凝胶工艺在氧化铝基体上制备的涂层由La_(1-x)Sr_xMnO_3单相组成。本研究范围内,随着粉体加入量的提高,薄膜厚度增加,但过多粉体使浆料的粘附性变差;分散剂的加入促进了浆料中粉体的均匀分散,但其高温分解也容易诱发薄膜的开裂;浸渍次数增加有利于提高薄膜厚度,但也延长了工艺流程;封孔后的薄膜更加平整,空洞明显减少;800℃以前有机物全部分解完成。
对不同的薄膜电性能研究表明,掺锶量对薄膜导电性的影响较为明显,本研究的掺锶量范围内(x=0.2、0.3、0.4和0.5),x=0.4时的导电性最好。粉体加入量的增加和增加的封孔工艺均可提高薄膜导电性。
在对比分析粉体加入量、分散剂、浸渍次数、封孔工艺和热处理温度等对薄膜组织影响的基础上,得出了制备高质量薄膜的几个最佳参数:粉体加入量62.0%;聚乙二醇作分散剂,加入量为0.2 ml;浸渍次数为6次;封孔次数2次;预烧温度为600℃,保温时间为10 min,终烧温度为800℃,保温时间为1h。另外,研究发现调节pH值到9.0可提高浆料的稳定性。
The perovskite material LaMO_3(M=Cr、Fe、Mn,et.al)which has obvious Negative Temperature Coefficient(NTC)characterization,could be used for the next generation material of the NTC thermally sensitive resistance.The resistance-temperature relationship could be controlled and the best performance could be achieved by such approach as doping.Due to the excellent high temperature performance and resistance-temperature characterization of LaMO_3 film,it is expected to be used as the next generation film material of thermo-sensitive,and exploit the direct contact type temperature probe that is resistant to acid,alkali and corrosive gas by being coated on the appropriate substrate.
The purpose of this thesis is to prepare La_(1-x)Sr_xMO_3(LSMO)film with dense structure and certain thickness on the Al_2O_3 substrate,and then study the electrical property of this kind of film.The structure,phase composition and surface and cross-section morphology of the films were analyzed by XRD,SEM testing methods et.al.The relationship between the processing parameters (including the concentration of the gel,the doped amount,the amount of the added powder,the plug densification,the dipping number,the presintering temperature,the sintering temperature and so on)and the structure of the film was studied;The electrical property of the La_(1-x)Sr_xMO_3 film was researched to find out the key processing parameter that determines the electrical property;And the formation mechanism of the LaMO_3 film and the electrical mechanism of the doped peroveskite structure was also studied.
Through systemic comparison,the composite sol-gel processing technology of preparing high quality La_(1-x)Sr_xMO_3 film on the Al_2O_3 substrate was optimized, the key of this processing technology is as follows:first,prepare doped La_(1-x)Sr_xMO_3 nano-powder and La_(1-x)Sr_xMO_3 gel that is of the same component as the powder;then,mix the powder and the gel with certain proportion to make the composite slurry;and finally,coat the pretreated substrate with dipping sliding method and sinter to form the film.The main processing parameters that affect the quality of the film are the amount of the powders added,the dispersant,the number of the dipping,the plug processing,the heat treatment temperature and so on.
It was shown by XRD and SEM that a single La_(1-x)Sr_xMO_3 perovskite phase was obtained on the Al_2O_3 substrate with the composite sol-gel methods.With the increase of the added amount of the powder,the thickness of the film increases, but the adhesiveness becomes worse when too much powder was added;the dispersant accelerates the uniform disperse of the powder in the slurry,but its decomposition under high temperature is inductive to crack the film;the increase of the dipping time is helpful to improve the thickness of the film,but also prolongs the processing flow;the film is smoother after plugging,the cavity decreases obviously,and all the organic substance decomposes completely before 800℃.
According to the study of the electrical property of different films,the amount of Sr dopped has a strong influence on the electrical property,within x=0.2,0.3,0.4,0.5,when x=0.4 the electrical property reaches its highest point. The increase of the added powder and the increase of the plug technology could increase the electrical property of the film.
Based on the comparison of the influence of the added amount of the powder, the dispersant,the number of dipping,the plug technology and heat treat temperature on the film,the optimized processing parameter is obtained,that is, the amount of added powder 62.0%,polyethylene glycol as dispersant agent, added amount 0.2ml,the number of dipping 6,plug twice,pre-sintering at 600℃for 10 min,sintering at 800℃for 1 h in air.In addition,it is found that the stability of the slurry could be greatly improved by the adjustment of the pH value to 9.0.
本研究的目的是在Al_2O_3基底上制备组织致密、且有一定厚度的La_(1-x)Sr_xMO_3薄膜,进而探讨此类薄膜的电性能。研究主要集中在:采用复合溶胶-凝胶方法制备La_(1-x)Sr_xMnO_3薄膜,用XRD、SEM等手段对不同薄膜的结构、相组成、表面和截面组织形貌进行分析,研究各工艺参数(包括前驱体溶液浓度、掺杂量、粉体加入量、封孔致密化、浸渍次数、预烧温度和烧结温度等)与薄膜组织的关系;研究La_(1-x)Sr_xMnO_3薄膜的电性能,找出决定电性能的关键工艺参数;探讨LaMO_3薄膜的形成机制、钙钛矿结构的掺杂导电机理等相关问题。
通过系统地对比研究,优选出了在Al_2O_3基底上制备高质量La_(1-x)Sr_xMO_3薄膜的复合溶胶-凝胶制备工艺,该工艺的关键为:首先制备掺锶锰酸镧纳米粉体和同组分的锰酸锶镧溶胶;然后将纳米粉体和溶胶按一定比例配合,制成复合浆料;最后采用浸渍提拉法在经预处理的基底上进行涂覆并煅烧成膜。在复合溶胶-凝胶制备工艺中,影响薄膜质量的主要因素为:粉体加入量、分散剂、浸渍次数、封孔工艺、热处理温度等。
XRD和SEM表征结果证明,用复合溶胶-凝胶工艺在氧化铝基体上制备的涂层由La_(1-x)Sr_xMnO_3单相组成。本研究范围内,随着粉体加入量的提高,薄膜厚度增加,但过多粉体使浆料的粘附性变差;分散剂的加入促进了浆料中粉体的均匀分散,但其高温分解也容易诱发薄膜的开裂;浸渍次数增加有利于提高薄膜厚度,但也延长了工艺流程;封孔后的薄膜更加平整,空洞明显减少;800℃以前有机物全部分解完成。
对不同的薄膜电性能研究表明,掺锶量对薄膜导电性的影响较为明显,本研究的掺锶量范围内(x=0.2、0.3、0.4和0.5),x=0.4时的导电性最好。粉体加入量的增加和增加的封孔工艺均可提高薄膜导电性。
在对比分析粉体加入量、分散剂、浸渍次数、封孔工艺和热处理温度等对薄膜组织影响的基础上,得出了制备高质量薄膜的几个最佳参数:粉体加入量62.0%;聚乙二醇作分散剂,加入量为0.2 ml;浸渍次数为6次;封孔次数2次;预烧温度为600℃,保温时间为10 min,终烧温度为800℃,保温时间为1h。另外,研究发现调节pH值到9.0可提高浆料的稳定性。
The perovskite material LaMO_3(M=Cr、Fe、Mn,et.al)which has obvious Negative Temperature Coefficient(NTC)characterization,could be used for the next generation material of the NTC thermally sensitive resistance.The resistance-temperature relationship could be controlled and the best performance could be achieved by such approach as doping.Due to the excellent high temperature performance and resistance-temperature characterization of LaMO_3 film,it is expected to be used as the next generation film material of thermo-sensitive,and exploit the direct contact type temperature probe that is resistant to acid,alkali and corrosive gas by being coated on the appropriate substrate.
The purpose of this thesis is to prepare La_(1-x)Sr_xMO_3(LSMO)film with dense structure and certain thickness on the Al_2O_3 substrate,and then study the electrical property of this kind of film.The structure,phase composition and surface and cross-section morphology of the films were analyzed by XRD,SEM testing methods et.al.The relationship between the processing parameters (including the concentration of the gel,the doped amount,the amount of the added powder,the plug densification,the dipping number,the presintering temperature,the sintering temperature and so on)and the structure of the film was studied;The electrical property of the La_(1-x)Sr_xMO_3 film was researched to find out the key processing parameter that determines the electrical property;And the formation mechanism of the LaMO_3 film and the electrical mechanism of the doped peroveskite structure was also studied.
Through systemic comparison,the composite sol-gel processing technology of preparing high quality La_(1-x)Sr_xMO_3 film on the Al_2O_3 substrate was optimized, the key of this processing technology is as follows:first,prepare doped La_(1-x)Sr_xMO_3 nano-powder and La_(1-x)Sr_xMO_3 gel that is of the same component as the powder;then,mix the powder and the gel with certain proportion to make the composite slurry;and finally,coat the pretreated substrate with dipping sliding method and sinter to form the film.The main processing parameters that affect the quality of the film are the amount of the powders added,the dispersant,the number of the dipping,the plug processing,the heat treatment temperature and so on.
It was shown by XRD and SEM that a single La_(1-x)Sr_xMO_3 perovskite phase was obtained on the Al_2O_3 substrate with the composite sol-gel methods.With the increase of the added amount of the powder,the thickness of the film increases, but the adhesiveness becomes worse when too much powder was added;the dispersant accelerates the uniform disperse of the powder in the slurry,but its decomposition under high temperature is inductive to crack the film;the increase of the dipping time is helpful to improve the thickness of the film,but also prolongs the processing flow;the film is smoother after plugging,the cavity decreases obviously,and all the organic substance decomposes completely before 800℃.
According to the study of the electrical property of different films,the amount of Sr dopped has a strong influence on the electrical property,within x=0.2,0.3,0.4,0.5,when x=0.4 the electrical property reaches its highest point. The increase of the added powder and the increase of the plug technology could increase the electrical property of the film.
Based on the comparison of the influence of the added amount of the powder, the dispersant,the number of dipping,the plug technology and heat treat temperature on the film,the optimized processing parameter is obtained,that is, the amount of added powder 62.0%,polyethylene glycol as dispersant agent, added amount 0.2ml,the number of dipping 6,plug twice,pre-sintering at 600℃for 10 min,sintering at 800℃for 1 h in air.In addition,it is found that the stability of the slurry could be greatly improved by the adjustment of the pH value to 9.0.
引文
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