CN103360064A - 铁电薄膜的制造方法和静电喷涂用液 - Google Patents
铁电薄膜的制造方法和静电喷涂用液 Download PDFInfo
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- CN103360064A CN103360064A CN2013100687902A CN201310068790A CN103360064A CN 103360064 A CN103360064 A CN 103360064A CN 2013100687902 A CN2013100687902 A CN 2013100687902A CN 201310068790 A CN201310068790 A CN 201310068790A CN 103360064 A CN103360064 A CN 103360064A
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Images
Classifications
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供铁电薄膜的制造方法和静电喷涂用液。在烧成通过静电喷涂吐出、形成的薄膜之后,得到致密且无龟裂的铁电薄膜。该方法为,从毛细管的吐出口朝向具有下部电极的基板的下部电极静电喷涂铁电薄膜形成用的静电喷涂用液而将静电喷涂用液涂布到下部电极上来形成涂膜,对该涂膜进行干燥、临时烧结之后进行烧成来使其结晶化,从而在下部电极上制造铁电薄膜。将静电喷涂用液设为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与该溶胶-凝胶液的固体物相同组成且具有可从吐出口吐出的粒径的粉末的混合液,且将溶解于溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将粉末的质量设为B时,将B相对于(A+B)的比率设为5%以上40%以下的范围。
Description
技术领域
本发明涉及一种利用静电喷涂法的铁电薄膜的制造方法,更详细而言,涉及一种利用静电喷涂装置及均匀混合铁电薄膜形成用溶胶-凝胶液和包含与该溶胶-凝胶液相同组成的粉末的分散液的混合液来制造致密且无龟裂的铁电薄膜的方法。
背景技术
DRAM(Dynamic Random Access Memory)、FeRAM(Ferroelectric Random AccessMemory)、RF电路等电子器件具备发挥作为电容器(condenser)的作用的电容器(capacitor),但是随着近几年对器件的小型化或高集成化的要求,电容器能够在器件内所占的面积也越来越窄。电容器具有上部电极、下部电极及介电层夹持于该两个电极之间的基本结构,电容器具有的静电容量与介电层的相对介电常数和电极的表面积成比例,另一方面,与两个电极间距离即介电层等的厚度成比例。由于限制介电层的厚度是有限的,因此为了在有限的占有面积中确保较高的静电容量,介电层需使用相对介电常数更高的介电材料。
因此,代替以往使用SiO2、Si3N4等的低介电常数的材料,由钛酸钡(BaTiO3)、钛酸锶钡(以下称为“BST”)、钛酸铅(以下称为“PT”)、锆钛酸铅(以下称为“PZT”)、在PZT中添加少量镧的镧添加锆钛酸铅(以下称为“PLZT”)等钙钛矿型氧化物形成的铁电薄膜受到关注。作为形成铁电薄膜的方法,目前为止,除了真空蒸镀法、溅射法或激光烧蚀法等物理气相沉积法或、CVD(Chemical Vapor Deposition)法等化学气相沉积法之外,一般广泛使用溶胶-凝胶法等化学溶液法(Chemical Solution Deposition、CSD法)。
尤其,与CVD法或溅射法等相比,溶胶-凝胶法无需真空工艺,因此具有制造成本较低且还容易在面积较广的基板上形成之类的优点。而且,通过改变用于形成铁电薄膜的溶液材料中的组成,容易使膜中的组成为理论比率,且可得到极薄的铁电薄膜,因此作为形成大容量的薄膜电容器等的方法而被期待。基于溶胶-凝胶法的制造方法中,通常,首先进行溶胶-凝胶液的制备,将该制备的溶胶-凝胶液涂布到基板上之后,通过以预定温度进行烧成等来得到铁电薄膜。目前为止,在基于上述溶胶-凝胶法的铁电薄膜的制造方法中,溶胶-凝胶液向基板上的涂布广泛使用旋涂法等。这是因为,旋涂法在基于溶胶-凝胶法的铁电薄膜的制造方法中,例如通过使基板高速旋转来以离心力去除液体,因此在可提高基板面内的膜厚均匀性的观点上优异。
但是,旋涂法中存在如下问题:即将溶胶-凝胶液涂布到基板上时,材料的大部分从基板上飞散而造成浪费,因此材料的利用效率非常差。因此,还研究了利用除旋涂法以外的方法的制造方法等,作为这种方法,已知有例如溶胶-凝胶液向基板上的涂布使用静电喷涂(Electrostatic Spray Deposition:以下称为ESD法)的铁电薄膜的制造方法。使用ESD法的铁电薄膜的制造方法中,向基板上涂布溶胶-凝胶液时,能够使从毛细管的吐出口喷射的溶胶-凝胶液的约90%左右堆积到基板上等,材料的利用效率非常高且成膜速度较快,因此尤其在批量生产性或制造成本方面受到关注。上述ESD法中,公开有如下方法:利用将溶解于溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A、将粉末的质量设为B时B相对(A+B)的比率为83%的静电喷涂用液,制作涂布60层来形成的28μm左右的厚膜的高密度PZT铁电薄膜(参考非专利文献1)。
非专利文献1:Journal of the European Ceramic Society(2008),pp.2739-2745
由非专利文献1所示的方法得到的薄膜中观察到致密且无龟裂的组织,但铁电薄膜中存在小于400nm的孔隙,铁电薄膜的表面不均匀,无法良好地成膜。
发明内容
鉴于所涉及的现状,发明人等如下进行深入研究的结果,实现了本发明:在基于ESD法的铁电薄膜的制造方法中使用的静电喷涂用液中也同样能够得到使用基于旋涂法的铁电薄膜的制造方法中适用的如上述的混合液时的优点。
本发明的目的在于提供一种铁电薄膜的制造方法及通过该方法得到的铁电薄膜,该铁电薄膜的制造方法中,在烧成通过静电喷涂吐出均匀混合铁电薄膜形成用溶胶-凝胶液和具有与该溶胶-凝胶液的固体物相同组成且具有可从吐出口吐出的粒径的粉末的混合液来形成的薄膜之后成为致密且无龟裂的铁电薄膜。
本发明的第1方案提供铁电薄膜的制造方法,其从毛细管的吐出口朝向具有下部电极的基板的所述下部电极静电喷涂铁电薄膜形成用的静电喷涂用液而将所述静电喷涂用液涂布到所述下部电极上来形成涂膜,对所述涂膜进行干燥、临时烧结之后进行烧成来使其结晶化,从而在所述下部电极上制造铁电薄膜,其特征在于,
所述静电喷涂用液为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与所述溶胶-凝胶液的固体物相同组成且具有可从所述吐出口吐出的粒径的粉末的混合液,其中,将溶解于所述溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于(A+B)的比率在5%以上40%以下的范围。
本发明的第2方案提供静电喷涂用液,其用于从毛细管的所述吐出口静电喷涂来形成铁电薄膜,其特征在于,均匀混合铁电薄膜形成用溶胶-凝胶液和与所述溶胶-凝胶液的固体物相同组成且具有可从所述吐出口吐出的粒径的粉末,将溶解于所述溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于(A+B)的比率在5%以上40%以下的范围。
本发明的第1方案的制造方法,从毛细管的吐出口朝向具有下部电极的基板的所述下部电极静电喷涂铁电薄膜形成用的静电喷涂用液而将所述静电喷涂用液涂布到所述下部电极上来形成涂膜,对所述涂膜进行干燥、临时烧结之后进行烧成来使其结晶化,从而在所述下部电极上制造铁电薄膜,其中,所述静电喷涂用液为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与所述溶胶-凝胶液的固体物相同组成且具有可从所述吐出口吐出的粒径的粉末的混合液,将溶解于所述溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于(A+B)的比率设定在5%以上40%以下的范围。其结果,在下部电极上成膜并通过临时烧结、烧成来制造的铁电薄膜成为其组织致密且无龟裂的薄膜。
本发明的第2方案的静电喷涂用液中,用于从毛细管的所述吐出口静电喷涂来形成铁电薄膜的静电喷涂用液,其中,均匀混合铁电薄膜形成用溶胶-凝胶液和与所述溶胶-凝胶液的固体物相同组成且具有可从所述吐出口吐出的粒径的粉末,将所述溶胶-凝胶液的质量设为A,将所述粉末的质量设为B时,B相对于(A+B)的比率设定在5%以上40%以下的范围。由此,成膜并通过临时烧结、烧成来制造的铁电薄膜成为致密且无龟裂的薄膜。
附图说明
图1是表示用于ESD法的一般装置的概要的示意图。
符号说明
10-静电喷涂装置,11-载物台,11a-导电层,12-注射器,13-泵,14-毛细管,14a-吐出口,16-高压电源装置,20-基板,20a-下部电极,21-混合液(静电喷涂用液)。
具体实施方式
接着,对用于实施本发明的方式分为<静电喷涂用液>和<使用静电喷涂用液的铁电薄膜的制造方法>来进行说明。
<静电喷涂用液>
本发明的静电喷涂用液为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与溶胶-凝胶液的固体物相同组成且具有可从所述吐出口吐出的粒径的粉末的混合液,其特征在于,将溶解于溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于(A+B)的比率在5%以上40%以下的范围。
以下,依次对静电喷涂用液所需的上述铁电薄膜形成用溶胶-凝胶液及上述粉末以及上述混合液进行说明。
首先,对铁电薄膜形成用溶胶-凝胶液进行说明。该铁电薄膜形成用溶胶-凝胶液由有机金属化合物溶液构成,该有机金属化合物溶液为用于构成复合金属氧化物的原料以赋予所希望的金属原子比的比例的方式包含溶解于有机溶剂中的有机金属化合物溶液。
复合金属氧化物原料优选为有机基团通过其氧或者氮原子与Pb、La、Zr及Ti的各金属元素键合的化合物。例如,例示选自金属醇盐、金属二醇络合物、金属三元醇络合物、金属羧酸盐、金属β-二酮络合物、金属β-二酮酯络合物、金属β-亚氨基酮络合物及金属氨基络合物中的一种或两种以上。尤其优选的化合物为金属醇盐、其部分水解物及有机酸盐。其中,作为Pb化合物、La化合物可以举出醋酸盐(醋酸铅:Pb(OAc)2、醋酸镧:La(OAc)3)、二异丙氧基铅:Pb(OiPr)2、三异丙氧基镧:La(OiPr)3等。作为Ti化合物可以举出四乙氧基钛:Ti(OEt)4、四异丙氧基钛:Ti(OiPr)4、四正丁氧基钛:Ti(OnBu)4、四异丁氧基钛:Ti(OiBu)4、四叔丁氧基钛:Ti(OtBu)4、二甲氧基二异丙氧基钛:Ti(OMe)2(OiPr)2等醇盐。作为Zr化合物优选与上述Ti化合物相同的醇盐类。金属醇盐可以直接使用,也可以为了促进分解而使用其部分水解物。
为了制备铁电薄膜形成用溶胶-凝胶液,将这些原料以相当于所希望的铁电薄膜组成的比率溶解于适当的溶剂中,调整成适于涂布的浓度。
在此使用的铁电薄膜形成用溶胶-凝胶液的适合的溶剂可根据所使用的原料适当决定,一般可以使用羧酸、醇(例如乙醇、1-丁醇或作为多元醇的丙二醇)、酯、酮类(例如丙酮、甲基乙基酮)、醚类(例如二甲基醚、二乙基醚)、环烷类(例如环己烷、环己醇)、芳香族系(例如苯、甲苯、二甲苯)、四氢呋喃等,或者能够使用这些的两种以上的混合溶剂。其中,根据蒸发速度和溶解性的观点,尤其优选1-丁醇、乙醇或丙二醇。
作为羧酸,具体优选使用n-丁酸、α-甲基丁酸、异戊酸、2-乙基丁酸、2,2-二甲基丁酸、3,3-二甲基丁酸、2,3-二甲基丁酸、3-甲基戊酸、4-甲基戊酸、2-乙基戊酸、3-乙基戊酸、2,2-二甲基戊酸、3,3-二甲基戊酸,2,3-二甲基戊酸、2-乙基己酸及3-乙基己酸。
并且,作为酯优选使用醋酸乙酯、醋酸丙酯、醋酸正丁酯、醋酸仲丁酯、醋酸叔丁酯、醋酸异丁酯、醋酸正戊酯、醋酸仲戊酯、醋酸叔戊酯及醋酸异戊酯,作为醇优选使用1-丙醇、2-丙醇、1-丁醇、2-丁醇、异丁醇、1-戊醇、2-戊醇、2-甲基-2-戊醇及2-甲氧基乙醇。
另外,优选铁电薄膜形成用溶胶-凝胶液的有机金属化合物溶液(溶胶-凝胶液)中的复合金属化合物原料的总计浓度设为10~25质量%。
该有机金属化合物溶液中,可以根据需要添加以(稳定剂分子数)/(金属原子数)计为0.2~3左右的、β-二酮类(例如乙酰丙酯、2,2-二甲基-6,6,7,7,8,8,8-七氟-3,5-辛二酮(Heptafluorobutanoyl pivaloylmethane)、二叔戊酰甲烷、三氟乙酰丙酮、苯甲酰丙酮等)、β-酮酸类(例如乙酰醋酸、丙酰醋酸、苯甲酰醋酸等)、β-酮酯类(例如上述酮酸的甲基、丙基、丁基等低级烷基酯类)、含氧酸类(例如乳酸、羟基乙酸、α-羟基丁酸、水杨酸等)、上述含氧酸的低级烷基酯类、羟基酮类(例如二丙酮醇、3-羟基丁酮等)、二醇、三元醇、高级羧酸、烷醇胺类(例如二乙醇胺、三乙醇胺、单乙醇胺)及多元胺等作为稳定剂。
并且,优选有机金属化合物溶液作为稳定剂包含多元醇类。其中,作为多元醇类尤其优选丙二醇。
优选对上述所制备的有机金属化合物溶液通过进行过滤处理等,去除粒子,将粒径为0.5μm以上(尤其0.3μm以上特别是0.2μm以上)的粒子的个数设为每1mL溶液中50个/mL以下。若有机金属化合物溶液中的粒径为0.5μm以上的粒子的个数超过50个/mL,则长期保存稳定性变差。该有机金属化合物溶液中的粒径为0.5μm以上的粒子的个数越少越优选,尤其优选为30个/mL以下。
以成为上述粒子个数的方式处理制备后的有机金属化合物溶液的方法没有特别限定,但例如可举出如下的方法。第1方法:使用市售的孔径为0.2μm的薄膜过滤器并用注射器挤压的过滤法。第2方法:组合市售的孔径为0.05μm的薄膜过滤器与加压罐的加压过滤法。第3方法:组合上述第2方法中使用的过滤器与溶液循环槽的循环过滤法。
任何一种方法中因溶液挤压压力而基于过滤器的粒子捕捉率均不同。通常已知压力越低捕捉率越变高,尤其是,在第1方法、第2方法中,为了实现将粒径为0.5μm以上的粒子个数设为50个以下的条件,优选使溶液以低压非常缓慢地通过过滤器。
接着,对上述粉末进行说明。该粉末的特征在于,具有与铁电薄膜形成用溶胶-凝胶液的固体物相同组成,且具有可从设置于图1所示的静电喷涂装置10的毛细管14前端的吐出口14a吐出的粒径。
例如,铁电薄膜形成用溶胶-凝胶液的固体物为PZT所涉及的组合物时,粉末也为与其相同组成的PZT所涉及的组合物。因此,将铁电薄膜形成用溶胶-凝胶液的固体物及粉末的Pb、Zr、Ti的组成比设为相同。并且,该粉末的粒子粒径不是可从吐出口14a吐出的粒径时会产生粉末堵塞吐出口14a等的不良情况而无法顺畅地进行静电喷涂。更详细而言,若假设吐出口14a的口径为150μm,则优选构成粉末的粒子粒径设为0.1μm~0.5μm。这是因为若超过0.5μm,则存在粉末堵塞吐出口14a的不良情况。
接着,对上述混合液进行说明。关于该混合液,在准备上述铁电薄膜形成用溶胶-凝胶液和上述粉末之后,将粉末作为分散质且将丁醇作为分散介质,使粉末分散于丁醇来制作分散液。此时,优选分散于丁醇的粉末的质量%相对丁醇100质量%为5质量%~40质量%。这是因为若小于5质量%或超过40质量%,则产生分散性降低的不良情况。
混合比率调整为将溶解于铁电薄膜形成用溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A、将所述粉末的质量设为B时,B相对于(A+B)的比率在5%以上40%以下的范围。这是因为若小于下限值,则存在易产生龟裂的不良情况,若超过上限值,则存在膜组织不会致密的不良情况。混合时,将两种液体适量投入到烧杯或罐等适当的容器,以铁电薄膜形成用溶胶-凝胶液的固体物与上述粉末均匀混合且均匀分散于混合液中的方式充分搅拌上述铁电薄膜形成用溶胶-凝胶液和上述粉末的分散液来得到静电喷涂用液。
<使用静电喷涂用液的铁电薄膜的制造方法>
本发明的铁电薄膜的制造方法中,通过ESD法一边喷射上述静电喷涂用液一边在预定的基板上进行铁电薄膜的成膜。以下参考图1对该制造方法进行说明。
作为制造铁电薄膜的基板,使用形成有下部电极的硅基板或蓝宝石基板等耐热性基板。作为形成于基板上的下部电极,使用Pt、Ir或Ru等具有导电性且不与铁电薄膜反应的材料。优选所制造的铁电薄膜为含Pb的钙钛矿型氧化物,可举出PZT或PLZT、PMnZT、PNbZT等。
本发明的铁电薄膜的制造方法中,例如使用图1所示的静电喷涂装置10(以下设为装置10),通过ESD法涂布静电喷涂用液21。图1所示的装置10中,设置有用于在静电喷涂中载置被涂装物即基板20等的载物台11,该载物台11表面设置有导电层11a。并且,具备用于积存成为原料的静电喷涂用液21的注射器12和用于挤压填充于注射器12内的静电喷涂用液21的泵13。并且,设置有用于朝向载置于载物台11的导电层11a上的基板20喷射从上述注射器12送出的静电喷涂用液21的金属制毛细管14。该毛细管14配置成设置于毛细管14前端的吐出口14a与载物台11表面对置。并且,载物台11设置成可上下移动,以便能够任意地调整吐出口14a与载置于载物台11的基板20等之间的距离。并且,设置有高压电源装置16,其用于对载物台11的导电层11a与从毛细管14即毛细管14的吐出口14a喷射的静电喷涂用液21施加直流高压。ESD法中,将载置于上述载物台11的基板20等被涂装物设为正极,将毛细管14设为负极,通过高压电源装置16施加直流高压从而在两极间形成静电场。并且,能够通过使带负电荷的雾状静电喷涂用液21吸附到带相反电荷的基板20等来高效地进行涂布。
为了使用ESD法制造铁电薄膜,首先将上述静电喷涂用液21填充到设置于上述装置10的注射器12内,并将具有下部电极20a的基板20载置于载物台11的导电层11a上。并且在通过高压电源装置16施加所希望的直流高压的状态下使泵13工作,来挤压填充于注射器12内的静电喷涂用液21。由此,从毛细管14的吐出口14a朝向基板20的下部电极20a以预定液量静电喷涂静电喷涂用液21,将静电喷涂用液21涂布到基板20的下部电极20a上。
本发明的铁电薄膜的制造方法中,通过静电喷涂将上述静电喷涂用液21喷出到基板20的下部电极20a上来涂布时,设定上述毛细管14的吐出口14a与载置于载物台11的基板20表面的下部电极20a之间的距离(以下称为基板间距离L)。此时,设定为上述涂膜的干燥、临时烧结后的折射率优选成为1.5以上,并且以一次喷涂来涂布静电喷涂用液,以临时烧结之后进行烧成来使其结晶化时的膜厚成为1000nm以下的方式设定一次喷涂中的静电喷涂用液的液量。由此能够制造致密的铁电薄膜。以上述涂膜的干燥、临时烧结之后的折射率成为1.5以上的方式设定基板间距离是为了使从毛细管的吐出口喷出的静电喷涂用液以保持所希望的湿气的状态堆积到基板上。认为若使静电喷涂用液以保持所希望的湿气的状态堆积到基板上,则能够得到具有所希望的膜组织的铁电薄膜的技术理由是因为非挥发成分与挥发成分以适当的比例堆积在基板上。另一方面,若使静电喷涂用液以几乎干燥的状态堆积到基板上,则非挥发成分成为粒子状而堆积到基板上,因此无法形成具有所希望的膜组织的铁电薄膜。关于从毛细管的吐出口喷出的静电喷涂用液,当基板间距离L越长,在到达基板之前静电喷涂用液中的溶剂成分等相应地蒸发,而以干燥的状态堆积。因此,为了使其以保持所希望的湿气的状态堆积到基板上,只要根据基板间距离L的实测值控制即可,但基板间距离L的实测值受因装置而产生的误差等影响较大,因此很难高精确度地控制用于得到良好膜质的基板间距离L。因此,本发明中,发现堆积到基板上的涂膜的湿气程度与形成于基板上的涂膜的干燥、临时烧结之后的折射率相关,通过根据该折射率高精确度地控制基板间距离L,能够使因装置而产生的误差等大幅下降。
若以干燥、临时烧结之后的折射率小于1.5的方式设定基板间距离L,则静电喷涂用液以几乎干燥的状态堆积到基板上,因此根据上述理由无法形成具有致密的膜组织的铁电薄膜。其中,优选以上述涂膜的干燥、临时烧结之后的折射率成为1.5~2.0的方式设定基板间距离L。另外,上述干燥、临时烧结之后的折射率是指在基板上涂布静电喷涂用液来形成涂膜之后,以后述的条件下使该涂膜干燥、临时烧结之后的折射率。
并且,以通过喷涂一次形成的烧成之后的薄膜的膜厚成为1000nm以下的方式设定喷涂一次静电喷涂用液的液量的理由在于,当将此时的液量设定为上述膜厚超过1000nm的量时,会发生产生龟裂或无法得到致密的组织的不良情况。其中优选上述液量设定为上述膜厚成为100~1000nm的范围的量。
并且,优选上述静电喷涂时的施加电压设定为15000~20000V的范围。若施加电压小于下限值,则很难稳定地对液体进行静电雾化。并且,静电喷涂时的气氛并未特别限定,可在大气气氛中进行。
并且,本发明的铁电薄膜的制造方法中,优选仅通过静电喷涂进行静电喷涂用液的涂布。本发明的制造方法中,通过以上述条件形成,无需并用通过旋涂法预先形成缓冲层等基于旋涂法的溶胶-凝胶液的涂布,就能够形成取向性优异的膜。因此,不仅与进行仅通过旋涂法进行涂布的方法相比,而且与并用旋涂法的方法相比,材料的利用效率较高,并且批量生产性也优异。
通过ESD法涂布静电喷涂用液来形成涂膜之后,对该涂膜进行干燥、临时烧结之后进行烧成来使其结晶化。干燥、临时烧结优选使用加热板等并在大气气氛中以150~550℃进行1~10分钟。
干燥、临时烧结是为了去除溶剂的同时对金属化合物进行热分解或水解来使其转化成复合氧化物而进行,因此优选在空气中、氧化气氛中或含水蒸气气氛中进行。即使在空气中进行加热,也可通过空气中的湿气充分确保水解所需的水分。该加热也可以以用于去除溶剂的低温加热和用于分解有机金属化合物的高温加热这两个阶段来实施。
另外,从通过ESD法涂布静电喷涂用液到干燥、临时烧结为止的工序可分别通过一次来进行,但优选多次反复到临时烧结为止的工序,以使成为所希望的膜厚,最后进行统一烧成。但是,认为若使用本发明的静电喷涂用液,则由于存在分散于溶液中的粉末,因此与以往的旋涂专用溶胶-凝胶液相比,到设为所希望的膜厚为止的上述次数可以更少。
烧成是用于以结晶化温度以上的温度对干燥、临时烧结之后的涂膜进行烧成来使其结晶化的工序,由此得到铁电薄膜。该结晶化工序的烧成气氛优选O2、N2、Ar、N2O或H2等或者它们的混合气体等。烧成以450~800℃进行1~60分钟左右。烧成可通过急速加热处理(RTA处理)进行。通过RTA处理进行烧成时,优选将其升温速度设为10~100℃/秒。
通过以上工序得到本发明的铁电薄膜。该铁电薄膜是通过利用ESD法的方法得到的薄膜。如此通过ESD法涂布的静电喷涂用液为铁电薄膜形成溶胶-凝胶液与粉末的混合液,且为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与该铁电薄膜形成用溶胶-凝胶液的固体物相同组成且具有可从吐出口14a吐出的粒径的粉末的混合液,将溶解于铁电薄膜形成用溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将粉末的质量设为B时,将B相对于(A+B)的比率设为5%以上40%以下的范围,从而混合液不会堵塞吐出口14a而能够顺畅地进行喷涂。并且,通过设为如上述的比率,能够在临时烧结、烧成之后制造致密且无龟裂的铁电薄膜。
并且,由于其为铁电薄膜,因此只要制造出致密且无龟裂的薄膜,就认为其具备与通过利用旋涂法的制造方法得到的薄膜相同程度的折射率及相对介电常数。
因此,本发明的铁电薄膜能够适当地用作薄膜电容器、电容器、IPD、DRAM存储器用电容器、层叠电容器、晶体管的栅极绝缘体、非易失性存储器、热释电型红外线检测元件、压电元件、电光元件、执行器、谐振器、超声波马达或LC噪声滤波器元件的复合电子组件中的构成材料。
[实施例]
接着,对本发明的实施例进行详细说明。
首先,在反应容器中加入四正丁氧基锆(Zr源)、异丙氧基钛(Ti源)及乙酰丙酮(稳定剂),在氮气氛下回流。接着,在该化合物中添加三水合乙酸铅(Pb源),并且添加丙二醇(溶剂),在氮气氛下回流,进行减压蒸馏来去除副产物之后,在该溶液中进一步添加丙二醇来调节浓度,再添加稀释醇,从而调整为复合金属氧化物材料在溶胶-凝胶液中所占的总计成为10质量%。由此,得到以氧化物换算计各金属比为Pb/Zr/Ti=110/52/48的铁电薄膜形成用溶胶-凝胶液。关于该溶胶-凝胶液,使用市售的孔径为0.2μm的薄膜过滤器,通过以注射器挤压过滤,粒径0.5μm以上的粒子个数分别为每1mL溶液中为1个。如此制备铁电薄膜形成用溶胶-凝胶液。
接着,准备由与上述的以氧化物换算计各金属比为Pb/Zr/Ti=110/52/48的铁电薄膜形成用溶胶-凝胶液相同组成构成的粉末。将粉末的平均粒径设为0.2μm。其中,粉末的最大粒径小于毛细管14的吐出口14a的口径,考虑间隙而将其设为0.5μm。将1g的该粉末投入到9g的1-丁醇中,充分搅拌使其分散到1-丁醇中。
接着,充分搅拌上述铁电薄膜形成用溶胶-凝胶液和上述粉末的分散液,以使铁电薄膜形成用溶胶-凝胶液的固体物与上述粉末均匀混合且在混合液中均匀分散,且将溶解于上述铁电薄膜形成用溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将上述粉末的质量设为B时,使B相对于(A+B)的比率成为20%,制作PZT(110/52/48)的混合液,将该混合液作为实施例中使用的静电喷涂用液。
接着,使用图1所示的装置10,在大气气氛中,通过ESD法在形成有下部电极20a的基板20的下部电极20a上形成铁电薄膜。具体而言,首先将上述制备的静电喷涂用液21填充到设置于上述装置10的注射器12内。并且,作为基板20,准备在其表面具有通过溅射法形成的厚度为0.2μm的Pt下部电极20a的硅基板20,将该基板20载置于装置10的载物台11的铝制导电层11a上。并且,在通过高压电源装置16施加所希望的直流高电压的状态下使泵13工作,来挤压填充到注射器12内的静电喷涂用液21,从毛细管14的吐出口14a朝向基板20的Pt下部电极20a以预定液量静电喷涂静电喷涂用液21。由此,将静电喷涂用液21涂布到基板20的Pt下部电极20a上来形成涂膜。
此时的具体条件如下设定。
将静电喷涂用液21的送液量设为5μl/分,将施加电压设为12000V,将从毛细管14的吐出口14a到基板为止的距离设为3cm,利用ESD装置10在基板20的下部电极20a上涂布5分钟上述制备的静电喷涂溶液之后,以300℃的加热板进行干燥、临时烧结,针对得到的带有凝胶膜的基板20进一步利用RTA以10℃/秒升温至700℃并保持1分钟。如此,本实施例中,形成由金属比为Pb/Zr/Ti=110/52/48的复合金属化合物构成的PZT铁电薄膜。
<评价>
关于实施例中得到的PZT铁电薄膜的评价,通过扫描电子显微镜SEM(S-4300SE、HITACHI制)进行膜厚测定以及表面观察和截面观察,观察表面组织及截面组织。并且,使用表面形状测定装置(Dektak150、Veeco制)测定PZT铁电薄膜的表面粗糙度Ra(μm),根据基于Ra值的膜表面的平滑度评价膜的致密度。并且,通过分光偏振光分析测定装置(M-2000D1,J.A.Woollam制)测定膜的折射率。
上述条件下,得到的PZT铁电薄膜的一层的膜厚为500nm,在表面发现50nm左右的微小且极少数的孔隙,但截面上不存在龟裂或孔隙。并且,得到的PZT铁电薄膜的表面粗糙度Ra为30nm左右,能够得到面极为平滑的膜。并且,得到的PZT铁电薄膜的折射率为1.9。
从以上实施例的结果可知,基于本发明的制造铁电薄膜的方法中,若使用如下静电喷涂用液,则能够通过ESD法在临时烧结、烧成之后得到致密且无龟裂的铁电薄膜,所述静电喷涂用液为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与铁电薄膜形成用溶胶-凝胶液的固体物相同组成且具有可从所述吐出口吐出的粒径的粉末的混合液,其中,将溶解于铁电薄膜形成用溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于(A+B)的比率在5%以上40%以下的范围。
产业上的可利用性
本发明可利用于薄膜电容器、电容器、IPD、DRAM储存器用电容器、层叠电容器、晶体管的栅极绝缘体、非易失性储存器、热释电型红外线检测元件、压电元件、电光元件、执行器、谐振器、超声波马达或LC噪声滤波器元件等的复合电子零件中的构成材料等的制造。
Claims (2)
1.一种铁电薄膜的制造方法,从毛细管的吐出口朝向具有下部电极的基板的所述下部电极静电喷涂铁电薄膜形成用的静电喷涂用液而将所述静电喷涂用液涂布到所述下部电极上来形成涂膜,对所述涂膜进行干燥、临时烧结之后进行烧成来使其结晶化,从而在所述下部电极上制造铁电薄膜,其特征在于,
所述静电喷涂用液为均匀混合铁电薄膜形成用溶胶-凝胶液和具有与所述溶胶-凝胶液的固体物相同组成且具有能从所述吐出口吐出的粒径的粉末的混合液,其中,
将溶解于所述溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于A+B的比率在5%以上40%以下的范围。
2.一种静电喷涂用液,其用于从毛细管的吐出口静电喷涂来形成铁电薄膜,其特征在于,
均匀混合铁电薄膜形成用溶胶-凝胶液和与所述溶胶-凝胶液的固体物相同组成且具有能从所述吐出口吐出的粒径的粉末,将溶解于所述溶胶-凝胶液中的金属化合物换算成金属氧化物的质量设为A,将所述粉末的质量设为B时,B相对于A+B的比率在5%以上40%以下的范围。
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CN112152510A (zh) * | 2020-09-25 | 2020-12-29 | 大连理工大学 | 一种以液滴为载体的热电荷动力循环系统 |
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CN107533161B (zh) * | 2015-11-20 | 2020-08-04 | Agc株式会社 | 带膜的弯曲基材及其制造方法以及图像显示装置 |
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JP7209952B2 (ja) * | 2018-07-05 | 2023-01-23 | 一般財団法人ファインセラミックスセンター | 強誘電体ナノ粒子集積方法及び電子部品の製造方法 |
TWI717651B (zh) * | 2018-11-06 | 2021-02-01 | 馗鼎奈米科技股份有限公司 | 壓電材料薄膜之製造方法與設備 |
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