CN108893723B - 一种快速制备超薄陶瓷片的方法 - Google Patents
一种快速制备超薄陶瓷片的方法 Download PDFInfo
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Abstract
本发明涉及一种快速制备超薄陶瓷片的方法，该方法利用激光化学气相沉积技术以相应的金属有机源作为前驱体原料，通过激光的活化作用在特定基板上沉积均匀的陶瓷层，然后通过烧蚀或研磨等手段将基板与制得的陶瓷层分离，最终得到单一、高致密的超薄特种陶瓷片。该方法不仅大幅降低了陶瓷片的烧结温度、有助于减少能耗，而且后处理程序简单、生产周期短、成本较低，在工业化生产方面具有巨大应用前景。
Description
技术领域
本发明涉及陶瓷材料技术领域，具体涉及一种快速制备超薄陶瓷片的方法。
背景技术
特种陶瓷是指具有特殊力学、物理或化学性能的陶瓷，其已广泛应用于各种现代工业和尖端科学技术中。特种陶瓷通常具有一种或多种功能，如电、磁、光、热、声、化学、生物等单一功能以及压电、热电、电光、声光、磁光等耦合功能，因此特种陶瓷成为了航空航天、能源、机械、电子信息和生物工程等尖端技术的基石。在二十一世纪的科学技术发展中，关于特种陶瓷方面的研究已占据十分重要的地位。
制备特种陶瓷所用到的原料和生产工艺技术与普通陶瓷有较大的不同，尤其是超薄特种陶瓷片的制备。现有技术中通常采用以下步骤制备特定厚度的超薄特种陶瓷：①制备原料粉体；②由原料粉体制备成型胚体；③高温烧结得到陶瓷制品；④磨削加工得到超薄特种陶瓷。上述方法虽然工艺较为简单，但是通常需要很高的烧结温度，设备和模具的费用较高，在高温烧结过程中难以获得成分单一的陶瓷制品，且表面及内部缺陷较多，晶粒较大，严重影响其性能。后期需要工艺复杂、耗时长、操作困难的磨削加工处理，并且在打磨过程中陶瓷制品容易断裂，导致整体制备成本较高。
激光化学气相沉积(Laser chemical vapor deposition，LCVD)技术是在传统化学气相沉积(chemical vapor deposition，CVD)技术上发展起来的，该技术以激光为辅助，通过激发气相物质分解和反应，从而在基板上快速沉积高质量的薄膜。LCVD使用的激光具备高能量密度及强方向性的特性，因此其具有以下优势：①制备的薄膜与基材结合更牢固，薄膜不易脱落；②沉积速率更快，LCVD沉积速率可达数百甚至数千微米/小时；③升温速率快，对基材性能损失小，变形度也小；④由于反应只发生在激光照射区域内，因此薄膜成分单一、纯度高、质量好；⑤沉积的薄膜均匀、平整；⑥反应室无需预加热,且沉积后处理工艺简单,可节约成本；⑦由于激光垂直照射在薄膜生长面上，因此薄膜受热均匀，沉积薄膜在500微米以上时仍然可以保持较好的生长情况，缺陷相对较少。
现阶段使用LCVD或CVD技术制备特种陶瓷薄膜的文献报道有很多。宋武林等人在《激光化学气相沉积TiC、TiN类陶瓷薄膜概况》中提到利用LCVD技术制备TiC、TiN类陶瓷薄膜的优势及LCVD技术的发展前景；孙红等人在《激光在化学气相沉积陶瓷膜中的应用》中概述了目前LCVD在制备陶瓷膜方面的广泛应用，其中使用的基板有金属、二氧化硅和单晶硅材料，并在这些基板上快速沉积了特种陶瓷薄膜，如AlN、TiC、BN等。综合来看，目前普遍是将通过LVCD技术制备的陶瓷薄膜与对应的基板结合在一起作为功能层使用，并没有直接得到完整、单一超薄陶瓷片的相关报道。
本发明使用LCVD技术首先在基板上沉积一层特种陶瓷薄膜并精确控制薄膜厚度，再通过特定技术手段(烧蚀或研磨等)将基板与特种陶瓷膜分离，从而得到了完整、成分单一的超薄特种陶瓷片。
发明内容
本发明的目的在于克服现有技术存在的上述不足，提供一种基于LCVD技术快速制备超薄特种陶瓷片的方法。该方法操作简单、效率高，制得的特种陶瓷片厚度薄、致密性高、无气孔、性能优异。为实现上述目的，本发明所采用的技术方案如下：
一种快速制备超薄特种陶瓷片的方法，包括以下步骤：
(a)将洗净、干燥后的基板放置在激光化学气相沉积装置的加热台上，然后抽真空并预热基板；
(b)调整激光化学气相沉积装置的沉积参数，在基板上沉积特种陶瓷层；
(c)将基板与沉积得到的特种陶瓷层分离，得到超薄特种陶瓷片。
进一步的，制得的超薄特种陶瓷片的厚度为400μm-3000μm。
进一步的，所述超薄特种陶瓷片包括大部分的氧化物陶瓷(如Al2O3、TiO2)、氮化物陶瓷(如AlN、BN、TiN)、碳化物陶瓷(如SiC)等。
进一步的，所述基板的材质包括石墨(C)、石英(SiO2)、单晶硅(Si)、YSZ(Y掺杂ZrO2单晶)等材料，基板厚度范围为0.5mm-400mm。
进一步的，步骤(a)具体过程如下：首先将基板依次置于丙酮、无水乙醇、去离子水中超声振荡清洗5-60min，然后将洗净的基板烘干并放置在激光化学气相沉积装置的加热台基板座上，抽真空使腔体压强降至50-10000Pa，同时将基板预热至323-1073K。
进一步的，步骤(b)中激光化学气相沉积的参数：沉积腔内部压强维持在50-5000Pa，载流气流量200-2000sccm，反应剂气体流量50-1000sccm，激光功率不超过10kW，激光波长为100nm-1000μm，激光光斑直径为10mm-100cm。载流气和保护气可选用Ar气等，反应剂气体可选用还原性的NH3和H2等。
进一步的，步骤(c)中基板与特种陶瓷层采用研磨、燃烧、化学腐蚀等方法进行分离。
优选的，所述基板为石墨材质，基板与特种陶瓷层采用燃烧的方法进行分离，燃烧室内压强控制在500-10000Pa，燃烧温度控制在473-873K，反应剂O2的流量控制在20-500sccm，燃烧时间为10-120min。
优选的，所述基板为单晶硅材质，基板与特种陶瓷层采用研磨法进行分离，通过研磨机将基板层磨去。
进一步的，步骤(c)中采用燃烧法分离出的超薄特种陶瓷片还需要使用由氨水和双氧水组成的混合溶液清洗，然后再使用氢氟酸水溶液超声清洗，最后用去离子水洗净并烘干。
与现有技术相比，本发明具有以下有益效果：
(1)避免了传统陶瓷烧结方法中存在的温度高、缺陷多、后处理工艺复杂等弊端，通过气相化学反应降低了陶瓷片成型所需的温度，同时还大幅提升了陶瓷片的沉积速率，沉积厚度可控(可精确到微米级)，后期无需复杂的机械处理过程；
(2)此外，通过该方法可制得单独的特种陶瓷片，避免了当前大多数类似方法只能得到基板-陶瓷片复合体的问题，拓展了特种陶瓷片的应用方式和范围；
(3)制得的特种陶瓷片制品性能优异，可满足多数应用器件的要求，生产周期短，效率高，成本较低，在大范围工业化生产应用方面前景巨大。
附图说明
图1为本发明工艺流程图。
图2为本发明实施例2制备的SiC特种陶瓷片样品的XRD图。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果，以下结合具体实施例及附图进行进一步说明。
图1为本发明方法的工艺流程图，其中①代表前驱体分子；②代表反应剂分子；③代表激光；④代表保护气分子；⑤代表薄膜生长层；⑥代表激光穿透层；⑦代表制备得到的陶瓷片层；⑧代表基板；⑨代表沉积完成后的基板-陶瓷片层复合结构；⑩代表去除基板的过程；
代表单独的超薄特种陶瓷片。
根据图1的工艺流程，基于LCVD技术快速制备超薄特种陶瓷片的方法具体如下：
(1)将基板材料依次置于丙酮、无水乙醇、去离子水中超声振荡清洗5-60min，然后将清洗干净的基板材料放在烘箱中充分干燥。烘干后的基板材料放置在激光化学气相沉积装置的加热台基板座上，抽真空并预热。
(2)取适量的金属有机源置于LCVD系统的原料缸中，维持反应腔体内气压为50-5000Pa，将激光发生器发射的连续激光照射在基板上，同时利用测温装置实时测量基板的温度。当基板温度稳定在沉积温度时，使用高纯Ar气作为载流气输送原料蒸气到反应腔体内，并对气体输送管道加热保温防止原料蒸气凝结。同时将反应剂气体通入反应腔体内，开始沉积。
(3)待陶瓷涂层沉积完成后，通过研磨、燃烧或化学腐蚀等手段将基板除去，得到超薄特种陶瓷片。
实施例1
利用LCVD技术在厚度为50mm的石墨基板上快速制备厚度为500μm的超薄AlN特种陶瓷片的方法如下：
(1)将石墨基板按照上述方法洗净干燥后放置于激光化学气相沉积装置的加热台基板座上，抽取真空至800Pa以下，然后将基板预热到773K。取适量Al(acac)3(三乙酰丙酮铝)溶于200mL的四氢呋喃溶剂中，将所得溶液加入到原料缸中。
(2)打开激光，将输出功率设置为180W，持续的Nd:YAG激光(波长为1064nm)透过设备的石英窗口照射到基板表面，形成约25mm左右的光斑。通过加热台背部的热电偶实时测量基板的温度，待温度升至1373K并稳定后，使用高纯Ar气作为载流气和保护气输送Al(acac)3蒸气，并对气体输送管道加热保温(473K)防止蒸气凝结。采用NH3作为反应剂气体，将其通入到反应腔体内，Ar气和NH3气流量分别控制在1200sccm和100sccm。当沉积条件设置完成后开始沉积，沉积时间为300min；沉积完成后在真空条件下自然冷却至室温。
(3)待AlN薄膜沉积完成后，将薄膜-基板复合体置于燃烧室内，加热至1073K，将烧结炉内抽真空至800Pa，通入流量为200sccm的O2，逐渐烧蚀基板，烧蚀时间约为60min。烧蚀完成后，取出薄膜样品将其置于氨水和双氧水的混合溶液中清洗，然后置于去离子水中超声震荡清洗，洗涤干净后置于烘箱中干燥，即得到厚度约为500微米的超薄AlN陶瓷片。
在沉积AlN陶瓷片的过程中，激光的增强作用主要包括两方面：热效应和光效应。光效应是当Al(acac)3气体分子与NH3分子进入到反应腔体后，在入射激光的作用下Al(acac)3气体分子与NH3分子吸收激光的光子能量直接转化为振动能量，当振动能量达到最大值时引发原子键断裂，在高温条件下迅速反应生成了AlN分子并沉积在基底上。光效应能够极大降低反应所需的活化能。热效应是利用激光照射到薄膜的生长层上并形成穿透层，在薄膜上形成了一个稳定均匀的能量场，持续稳定的为薄膜生长提供热量，由此大幅降低反应所需的加热温度。同时由于薄膜垂直于基板纵向生长，激光的热能供给可以避免薄膜生长的厚度增大带来的热量传输不均匀问题，从而可以保证薄膜在生长到500μm厚度时整体产生的缺陷仍然较少，从而极大提升沉积的薄膜质量。
实施例2
利用LCVD技术在厚度为100mm的石墨基板上快速制备厚度为450μm的SiC超薄特种陶瓷片的方法如下：
(1)首先将石墨基板依次置于丙酮、无水乙醇、去离子水中超声振荡清洗20min，然后将洗净的基板放在烘箱中充分干燥。将洗净后的石墨基板放入激光化学气相沉积装置的加热台基板座上，抽真空使压强降到800Pa以下，接着将基板预热至773K。取适量的六甲基二硅烷(C6H18Si2)溶于约200mL的四氢呋喃(Tetrahydrofuran；THF)溶剂中，将所得溶液加入到原料缸中。
(2)打开激光，将输出功率设置为180W，持续的Nd:YAG激光(波长为1064nm)透过设备的石英窗口照射在基板表面，形成约50mm左右的光斑。待基板温度升至1473K并保持稳定后，使用高纯Ar气作为保护气和载流气输送原料蒸气，并对气体输送管道加热保温(473K)防止蒸气凝结。采用H2作为还原剂气体，将其通入到反应腔体内，Ar气和H2气流量分别设定为1200sccm和50sccm。当沉积条件设置完成后开始沉积，沉积时间为60min；沉积完成后在真空条件下自然冷却至室温。
(3)待SiC薄膜沉积完成后，将薄膜-基板复合体置于烧结炉内并加热至573K，将烧结炉内抽真空至1kPa以下，通入流量为200sccm的O2，逐渐烧蚀基板，烧蚀时间约为90min。烧蚀完成后，取出SiC超薄特种陶瓷样品，将其置于氨水和双氧水的混合溶液中清洗，然后置于氢氟酸水溶液中超声清洗，最后用去离子水洗涤干净后用烘箱干燥，即得到厚度约为450μm的超薄SiC陶瓷片。
本实施例制得SiC超薄特种陶瓷片样品的XRD图如图2所示。从图2中可以看出，该样品材料的衍射峰与SiC的衍射峰相匹配。
Claims (5)
1.一种快速制备超薄特种陶瓷片的方法，其特征在于，包括以下步骤：
(a)将洗净、干燥后的基板放置在激光化学气相沉积装置的加热台上，然后抽真空并预热基板；
(b)调整激光化学气相沉积装置的沉积参数，在基板上沉积特种陶瓷层；
(c)将基板与沉积得到的特种陶瓷层分离，得到超薄特种陶瓷片；
所述基板为厚度0.5mm-400mm的石墨材质，基板与特种陶瓷层采用燃烧的方法进行分离，燃烧室内压强控制在500-10000Pa，燃烧温度控制在473-873K，反应剂O2的流量控制在20-500sccm，燃烧时间为10-120min；采用燃烧法分离得到的超薄特种陶瓷片先用由氨水和双氧水组成的混合溶液清洗，然后再使用氢氟酸水溶液超声清洗，最后用去离子水洗净并烘干；
或者所述基板为厚度0.5mm-400mm的单晶硅材质，基板与特种陶瓷层采用研磨法进行分离，通过研磨机将基板层磨去。
2.如权利要求1所述的一种快速制备超薄特种陶瓷片的方法，其特征在于：制得的超薄特种陶瓷片的厚度为400μm-3000μm。
3.如权利要求1所述的一种快速制备超薄特种陶瓷片的方法，其特征在于：所述超薄特种陶瓷片选自氧化物陶瓷、氮化物陶瓷、碳化物陶瓷中的一种。
4.如权利要求1所述的一种快速制备超薄特种陶瓷片的方法，其特征在于，步骤(a)具体过程如下：首先将基板依次置于丙酮、无水乙醇、去离子水中超声振荡清洗5-60min，然后将洗净的基板烘干并放置在激光化学气相沉积装置的加热台基板座上，抽真空使腔体压强降至50-10000Pa，同时将基板预热至323-1073K。
5.如权利要求1所述的一种快速制备超薄特种陶瓷片的方法，其特征在于，步骤(b)中激光化学气相沉积的参数为：沉积腔内部压强维持在50-5000Pa，载流气流量200-2000sccm，反应剂气体流量50-1000sccm，激光功率不超过10kW，激光波长为100nm-1000μm，激光光斑直径为10mm-100cm。
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