CN111902929A - 用于含金属材料的高压退火处理 - Google Patents

用于含金属材料的高压退火处理 Download PDF

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CN111902929A
CN111902929A CN201980016419.7A CN201980016419A CN111902929A CN 111902929 A CN111902929 A CN 111902929A CN 201980016419 A CN201980016419 A CN 201980016419A CN 111902929 A CN111902929 A CN 111902929A
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metal
containing layer
layer
substrate
oxygen
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考施·K·辛格
石美仪
斯里尼瓦斯·D·内曼尼
怡利·Y·叶
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Applied Materials Inc
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Abstract

本公开内容提供了用于在TFT显示应用、半导体、或存储器应用中在含金属层上执行退火处理的方法。在一个实例中，一种在基板上形成含金属层的方法包括以下步骤：在处理腔室中的基板上供应含氧气体混合物，所述基板包括设置在光学透明基板上的含金属层；将所述处理腔室中的所述含氧气体混合物维持在约2巴和约50巴之间的处理压力下；和在所述含氧气体混合物存在的情况下热退火所述含金属层。

Description

用于含金属材料的高压退火处理
技术领域
本发明的实施方式大体涉及用于在可以利用在TFT装置结构、半导体、或存储器应用中的膜堆叠中形成含金属层的方法。
背景技术
显示装置已经被广泛地用于范围广泛的电子应用，诸如TV、监控器、手机、MP3播放器、电子书阅读器、及个人数字助理(PDA)和类似者。显示装置一般被设计为用于藉由向液晶施加电场来产生所需的图像，该液晶填充两个基板之间的间隙且具有控制介电场强度的各向异性的介电常数。藉由调整透射通过基板的光的量，可以高效地控制光和图像的强度、品质、和功耗。
可以将各种不同的显示装置(诸如有源矩阵液晶显示器(AMLCD)或有源矩阵有机发光二极管(AMOLED))采用为利用触摸屏面板的显示装置的光源。在制造TFT装置时，具有高电子迁移率、低泄漏电流、和高击穿电压的电子装置会允许更多像素面积用于光透射和电路系统的集成，因此造成更亮的显像、更高的整体电效率、更快速的响应时间、和更高分辨率的显像。形成于装置中的低膜品质的材料层(诸如具有杂质的金属电极层)通常造成了不良的装置电气性能和短的装置使用寿命。因此，对于提供具有低的膜泄漏的装置结构，用于在TFT装置中形成膜层及将膜层与TFT装置集成在一起的稳定及可靠的方法变得至关重要，且需要高的击穿电压以供用于制造具有较低阈值电压偏移的电子装置和改善电子装置的整体性能。
因此，需要改善的材料以用于制造产生改善的装置电气性能和装置稳定性的TFT装置。
发明内容
本公开内容提供了用于在TFT显示应用、半导体、或电阻式随机存取存储器(resistive random access memory，ReRAM)中在含金属层上执行退火处理的方法。在一个实例中，一种在基板上形成含金属层的方法包括以下步骤：在处理腔室中的基板上供应含氧气体混合物，所述基板包括设置在光学透明基板上的含金属层；将所述处理腔室中的所述含氧气体混合物维持在2巴(bar)和50巴之间的处理压力下；和在所述含氧气体混合物存在的情况下热退火所述含金属层。
在另一个实例中，一种用于致密化设置在基板上的含金属层的方法包括以下步骤：在大于2巴的压力下热处理设置在光学透明基板上的含金属层；和在热处理介电层期间将基板温度维持在小于500摄氏度。
在又一个实例中，一种用于致密化设置在基板上的含金属层的方法包括以下步骤：在基板上形成含金属层；将掺杂物注入(implanting)到所述含金属层中；以及在将基板温度维持在小于500摄氏度的同时，在大于2巴的压力下热处理所述基板上的所述含金属层。
附图说明
可通过参照实施方式来详细理解本发明的上述特征以及上文简要概述的本发明的更具体描述，这些实施方式中的一些被绘示在附图中。然而，应注意，附图仅绘示本发明的典型实施方式且因此不应将其视为对本发明的范围的限制，因为本发明可以允许其他同等有效的实施方式。
图1是根据一些实施方式的处理腔室的简化正面截面图，所述处理腔室具有设置在其中的盒(cassette)；
图2是群集系统，可以将图1的处理腔室合并到所述群集系统中；
图3是薄膜晶体管装置结构的一个实例的截面图；和
图4是薄膜晶体管装置结构的另一个实例的截面图。
图5描绘根据一些实施方式的在含金属材料中执行的退火处理的流程图；
图6A-6D描绘根据一些实施方式的图5的用于将含金属材料热退火的顺序的一个实施方式。
为了便于理解，已经尽可能使用相同的参考标号(诸如类似退火条件下的大气压力下的退火)来标示各图共有的相同元件。所预期的是，可以有益地将一个实施方式的元件及特征并入其他实施方式而无需进一步叙述。
然而，要注意，附图仅绘示本发明的示例性实施方式，且因此不应将这些附图视为对本发明的范围的限制，因为本发明可以允许其他同等有效的实施方式。
具体实施方式
本公开内容的实施方式大致提供了一种TFT装置结构和在所述TFT装置结构中的源极、漏极、界面、和接触区域的有源层上执行热退火处理以便增强显示装置的电气性能的方法。其他的应用(包括半导体或存储器装置制造处理)也可以利用本文中所述的实施方式。热退火处理可以致密化基板上的金属电极、源极/漏极和/或接触区域、和/或膜层的有源层膜性质。在一个实例中，执行热处理处理以提供含金属层的热能，诸如含金属层(例如有源层)或金属电极层(例如金属栅极电极、源极-漏极和/或接触区域或电极层、或其他合适的金属结构)形成于TFT装置中。热退火处理可以致密化或最小化有源层膜结构中的氧缺乏，以向装置结构提供良好的品质、界面管理、和热稳定。热退火处理也可以增加含金属材料的结晶度，从而改善含金属层的电气性能。因此，显示装置中的源极/漏极和/或接触区域的金属电极和有源层所需的膜性质可以高效地增强晶体管和二极管装置的电气性能。
图1是用于单个基板的高压退火处理的单基板处理腔室100的简化正面截面图。单基板处理腔室100具有主体110，所述主体具有包封内部容积115的外表面112和内表面113。在诸如图1中的一些实施方式中，主体110具有环状截面，然而在其他实施方式中，主体110的截面可以是矩形或任何封闭的形状。主体110的外表面112可由抗腐蚀钢(CRS)(诸如但不限于不锈钢)制成。一个或更多个热屏蔽件(heat shield)125设置在主体110的内表面113上，所述热屏蔽件防止热量从单基板处理腔室100损失到外部环境中。主体110的内表面113以及热屏蔽件125可由镍基钢合金制成，所述镍基钢合金展现高度的腐蚀抗性，诸如但不限于
Figure BDA0002659919300000031
和
Figure BDA0002659919300000032
基板支撑件130设置在内部容积115内。基板支撑件130具有棒(stem)134和由杆134所保持的基板支撑构件132。杆134穿过形成为通过腔室主体110的通路122。连接至致动器138的棒(rod)139穿过形成为通过腔室主体110的第二通路123。棒139耦接至具有孔136的板135，所述孔容纳基板支撑件130的杆134。升降销137连接至基板支撑构件132。致动器138致动棒139，使得板135上下移动以与升降销137连接和断开。随着升降销137升高或降低，基板支撑构件132在腔室100的内部容积115内升高或降低。基板支撑构件132具有嵌入在中心内的电阻式加热元件131。电源133被配置为向电阻式加热元件131供电。电源133以及致动器138的操作由控制器180控制。
单基板处理腔室100在主体110上具有开口111，通过所述开口，可以向设置在内部容积115中的基板支撑件130装载和从所述基板支撑件130卸载一个或更多个基板120。开口111在主体110上形成隧道121。狭缝阀128被配置为可密封地封闭隧道121，使得只有在狭缝阀128开启时才能够进出开口111和内部容积115。高压密封件127被用来将狭缝阀128密封到主体110，以密封内部容积115以供进行处理。高压密封件127可由聚合物制成，例如含氟聚合物，诸如但不限于全氟弹性体和聚四氟乙烯(PTFE)。高压密封件127可进一步包括弹簧构件以供偏压密封件以改善密封性能。冷却沟道124设置在隧道121上、在高压密封件127附近，以在处理期间将高压密封件127维持低于高压密封件127的最大安全操作温度。可以将来自冷却流体源126的冷却剂(诸如但不限于惰性、介电、和高性能传热流体)在冷却沟道124内循环。来自冷却流体源126的冷却剂的流量是藉由控制器180通过从温度传感器116或流量传感器(未示出)所接收的反馈来控制的。环状热扼流器(thermal choke)129围绕隧道221而形成以防止来自内部容积115的热在缝阀128开启时流过开口111。
单基板处理腔室100具有通过主体110的端口117，所述端口流体连接至流体回路190，所述流体回路连接气体面板150、冷凝器160、和端口117。流体回路190具有气体导管192、源导管157、入口隔离阀155、排气导管163、和出口隔离阀165。许多加热器196、158、152、154、164、166与流体回路190的不同部分界面连接。许多温度传感器151、153、119、167、及169也被安置在流体回路190的不同部分处，以进行温度测量和向控制器180发送信息。控制器180使用温度测量信息来控制加热器152、154、158、196、164、及166的操作，使得流体回路190的温度被维持在高于设置在流体回路190和内部容积115中的处理流体的冷凝点的温度。
气体面板150被配置为在内部容积115的压力之下提供处理流体。引入到内部容积115中的处理流体的压力被耦接至主体110的压力传感器114监控。冷凝器160流体耦接至冷却流体源(未示出)且被配置为冷凝通过气体导管192离开内部容积115的气相处理流体。冷凝的处理流体接着被泵176移除。一个或更多个加热器140设置在主体110上且被配置为加热单基板处理腔室100内的内部容积115。加热器140、152、154、158、196、164、及166在通往冷凝器160的出口隔离阀165开启的同时将流体回路190内的处理流体保持为气相，以防止流体回路内的冷凝。
控制器180控制单基板处理腔室100的操作。控制器180控制气体面板150、冷凝器160、泵170、入口隔离阀155、出口隔离阀165、电源133及145的操作。控制器180还通信地连接至温度传感器116、压力传感器114、致动器138、冷却流体源126、和温度读数装置156及162。
处理流体可包括含氧气体和/或含氮气体、和/或硫族或碲(诸如S、Se、Te)气体或蒸气，诸如氧气、干蒸汽、水、过氧化氢、氨、S蒸气、Se蒸气、H2S、H2Se等等。处理流体可以与基板上的金属材料起反应以形成金属氮氧化物、金属氧化物、金属氧硫族元素化物(metaloxychalcogenide)、或金属硫族化物。替代于或附加于含氧气体和/或含氮气体，处理流体可包括含硅气体。含硅气体的实例包括有机硅、正硅酸四烷基酯气体和二硅氧烷。有机硅气体包括具有至少一种碳-硅键的有机化合物的气体。正硅酸四烷基酯气体包括由附接到SiO4 4-离子的四个烷基组成的气体。更具体而言，所述一种或更多种气体可以是(二甲基甲硅烷基)(三甲基甲硅烷基)甲烷((Me)3SiCH2SiH(Me)2)、六甲基二硅烷((Me)3SiSi(Me)3)、三甲基硅烷((Me)3SiH)、三甲基甲硅烷基氯((Me)3SiCl)、四甲基硅烷((Me)4Si)、四乙氧基硅烷((EtO)4Si)、四甲氧基硅烷((MeO)4Si)、四(三甲基甲硅烷基)硅烷((Me3Si)4Si)、(二甲基胺基)二甲基硅烷((Me2N)SiHMe2)、二甲基二乙氧基硅烷((EtO)2Si(Me)2)、二甲基二甲氧基硅烷((MeO)2Si(Me)2)、甲基三甲氧基硅烷((MeO)3Si(Me))、二甲氧基四甲基二硅氧烷(((Me)2Si(OMe))2O)、三(二甲基胺基)硅烷((Me2N)3SiH)、双(二甲基胺基)甲基硅烷((Me2N)2CH3SiH)、二硅氧烷((SiH3)2O)、及上述各者的组合。
在基板120的处理期间，高压区域115的环境被维持在将高压区域内的处理流体维持在气相的温度及压力下。此类压力及温度是基于处理流体的组成来选定的。在蒸气的情况下，温度及压力被保持在将蒸气维持在干蒸气状态的条件下。在一个实例中，高压区域115被加压到大于大气的压力，例如大于约2巴。在另一个实例中，高压区域115被加压到从约10到约50巴(例如从约20到约50巴之间)的压力。在另一个实例中，高压区域115被加压到高达约100巴的压力。在处理期间，高压区域115也被维持在高温下，例如超过225摄氏度的温度(由设置在盒150上的基板155的热预算所限制)，例如在约300摄氏度到约500摄氏度之间。
图2是示例性处理系统200的示意性俯视平面图，所述处理系统包括并入及集成在所述处理系统中的处理腔室(诸如图1中所绘示的处理腔室100)中的一者或更多者。在一个实施方式中，处理系统200可以是可从位于加州圣克拉拉市的应用材料公司(AppliedMaterials，Inc.)购得的
Figure BDA0002659919300000061
或
Figure BDA0002659919300000062
集成处理系统。预期的是，可以将其他的处理系统(包括来自其他制造商的那些处理系统)调适为受益于本公开内容。
系统200包括真空气密处理平台204、工厂界面202、及系统控制器244。平台204包括多个处理腔室100、212、232、228、220(诸如图1中所描绘的处理腔室100中的一个处理腔室)、以及耦接至真空基板传递腔室236的至少一个装载锁定腔室(load lock chamber)222。图2中示出了两个装载锁定腔室222。工厂界面202通过装载锁定腔室222耦接至传递腔室236。
在一个实施方式中，工厂界面202包括至少一个机座(docking station)208和至少一个工厂界面机械手214以促进基板的传递。机座208被配置为接受一个或更多个前开式标准舱(front opening unified pod，FOUP)。图2的实施方式中示出了两个FOUP 206A-B。具有设置在机械手214的一端上的叶片216的工厂界面机械手214被配置为从工厂界面202通过装载锁定腔室222向处理平台204传递基板以供进行处理。可选地，可以将一个或更多个计量站(metrology station)518连接至工厂界面202的终端226，以促进测量来自FOUP206A-B的基板。
装载锁定腔室222的每一者具有耦接至工厂界面202的第一端口和耦接至传递腔室236的第二端口。装载锁定腔室222耦接至压力控制系统(未示出)，所述压力控制系统将装载锁定腔室222抽空及通气以促进在传递腔室236的真空环境与工厂界面202的实质周围(例如大气)环境之间传递基板。
传递腔室236具有设置在其中的真空机械手230。真空机械手230具有叶片234，所述叶片能够在装载锁定腔室222、计量系统210、及处理腔室212、232、228、220之中传递基板224。
在系统200的一个实施方式中，系统200可包括一个或更多个处理腔室100、212、232、228、220，所述一个或更多个处理腔室可以是退火腔室(例如高压退火腔室、RTP腔室、激光退火腔室)、沉积腔室、蚀刻腔室、清洁腔室、固化腔室、或其他类似类型的半导体处理腔室。在系统200的一些实施方式中，处理腔室100、212、232、228、220、传递腔室236、工厂界面202、和/或装载锁定腔室222中的至少一者中的一者或更多者。
系统控制器244耦接至处理系统200。系统控制器244(其可包括计算装置201或被包括在计算装置201内)使用系统200的处理腔室100、212、232、228、220的直接控制来控制处理系统200的操作。或者，系统控制器244可以控制与处理腔室100、212、232、228、及系统200相关联的计算机(或控制器)。操作时，系统控制器244也允许来自各个腔室的数据收集和反馈以最佳化系统200的性能。
与上述的计算装置201非常相似，系统控制器244一般包括中央处理单元(CPU)238、存储器240、和支持电路242。CPU 238可以是可以用在工业环境中的任何形式的通用计算机处理器中的一者。支持电路242常规上耦接至CPU 238，且可包括高速缓冲存储器(cache)、时钟电路、输入/输出子系统、电源和类似者。软件程序将CPU 238转换成专用计算机(控制器)244。也可以由定位在系统200远端的第二控制器(未示出)存储和/或执行软件程序。
图3描绘TFT装置350的实例，所述TFT装置包括含金属层，所述含金属层可以在高压退火腔室中经历热退火处理，诸如图1中所描绘的高压退火处理100，可以将所述高压退火腔室合并到图2中所描绘的系统200中。薄膜晶体管装置结构350是设置在基板301上的底栅TFT结构。注意，基板301可以具有先前形成在所述基板上的膜、结构、或层的不同组合以促进在基板301上形成不同的装置结构或不同的膜堆叠。在一个实例中，基板301可以具有形成于所述基板上的装置结构350，如图3中所示。或者，基板301可以具有设置于所述基板上的另一种装置结构450，如图4中进一步示出的，将在下文进一步描述所述装置结构。基板301可以是玻璃基板、塑料基板、聚合物基板、金属基板、单个基板、卷对卷基板、或用于在其上形成薄膜晶体管的其他合适的透明基板中的任一者。
栅极电极层302被形成及图案化在基板301上，之后是栅极绝缘层304。在一个实施方式中，可以由任何合适的金属材料制造栅极电极层302，例如铝(Al)、钨(W)、铬(Cr)、钽(Ta)、钼(Mo)、铜(Cu)、或上述各者的组合。栅极绝缘层304的合适材料包括氧化硅(SiO2)、氮氧化硅(SiON)、氮化硅(SiN)和类似者。注意，图3中所描绘的薄膜晶体管装置结构350是底栅装置结构，其中栅极电极层302被形成于装置结构350的底部上。
有源层306被形成于栅极绝缘层304上。用于有源层306的材料可以选自具有高电子迁移率且适用于低温制造的透明金属氧化物材料，这允许在不损坏基板的情况下在低温下处理柔性基板材料(诸如塑料材料)。可以用于有源层306的材料的合适实例包括a-IGZO(非晶铟镓锌氧化物)、InGaZnON、ZnO、ZnON、ZnSnO、CdSnO、GaSnO、TiSnO、CuBO2、CuAlO2、CuGaO2、SrCuO、LaCuOS、GaN、InGaN、AlGaN、或InGaAlN等等。
在形成有源层306之后，可以将阻挡层308形成于有源层306上。可以由含金属材料形成阻挡层308，以便向后续形成于所述阻挡层上的金属电极层310(例如针对源极-漏极电极)提供良好的界面粘附以及良好的阻挡性质(例如扩散阻挡)。可以将阻挡层308图案化为在有源层306上形成所需的图案以促进在后续的蚀刻处理中将特征转移在设置在基板301上的膜层上。尽管如图3中所描绘的阻挡层308被图案化为所需的图案，但注意，阻挡层308可以呈现任何形式，根据需要包括装置结构350中的整个连续空白膜或任何不同的特征，只要阻挡层308可以高效地提供阻挡/扩散阻挡性质以防止来自有源层306的元素扩散到金属电极层310中，反之亦然。在一个实施方式中，阻挡层308可以是由金属介电层(诸如根据需要是Ta2Os或TiO2或任何合适的金属介电层)制造的单层的含金属介电层，如图3中所描绘的。在另一个实施方式中，阻挡层308可以根据需要呈现复合膜的形式。
在将金属电极层310(诸如源极-漏极金属电极层)设置在阻挡层308上方之后，随后，执行蚀刻处理以在金属电极层310中形成沟道320。在蚀刻之后，绝缘材料层314(诸如钝化层)接着被形成在金属电极层310上方以完成形成薄膜晶体管装置结构350的处理。
在一个实施方式中，可以用作金属电极层310的材料的实例包括铜(Cu)、金、银(Ag)、铝(Al)、钨(W)、钼(Mo)、铬(Cr)、钽(Ta)、上述各者的合金、及上述各者的组合。可以用作绝缘材料层314的合适材料包括氧化硅(SiO2)、氮氧化硅(SiON)、或氮化硅(SiN)和类似者。
图4描绘可以形成于基板301上的顶栅低温多晶硅(LTPS)TFT装置结构450的实例，而不是图3中所描绘的底栅装置结构350。LTPS TFT装置450是构建有有源层452的MOS装置，所述有源层包括形成于光学透明基板301上的源极区域409a、沟道区域408、和漏极区域409b(例如，或称为金属接触区域或源极-漏极金属触点)，其中将或不将可选的绝缘层404设置在所述光学透明基板上。在一个实例中，可以由透明的含金属层(诸如金属氧化物材料)制造包括源极区域409a、沟道区域408、和漏极区域409b的有源层，所述透明的含金属层具有高的电子迁移率及适于低温制造，这允许在不损坏基板的情况下在低温下处理柔性基板材料(诸如塑料材料)。可以用于源极区域409a、沟道区域408、和漏极区域409b的此类材料的合适实例包括a-IGZO(非晶铟镓锌氧化物)、掺杂的IGZO、InGaZnON、ZnO、ZnON、ZnSnO、CdSnO、GaSnO、TiSnO、CuBO2、CuAlO2、CuGaO2、SrCuO、LaCuOS、GaN、InGaN、AlGaN、或InGaAlN等等。
栅极绝缘层406接着被沉积于沉积的多晶硅层的顶部上，以将设置在所述栅极绝缘层上的阻挡层411和金属电极层414(诸如栅极电极)与沟道区域408、源极区域409a、和漏极区域409b隔离。可以由含金属材料形成阻挡层411，以便向后续形成于所述阻挡层上的金属电极层414(例如，栅极电极)提供良好的界面粘附以及良好的阻挡性质(例如扩散阻挡)。可以将阻挡层411图案化为在栅极绝缘层406上形成所需的图案以促进在后续的蚀刻处理中将特征转移在设置在基板102上的膜层上。阻挡层411可以高效地提供阻挡/扩散阻挡性质，以防止来自栅极绝缘层406的元素扩散到金属电极层414中，反之亦然。在一个实施方式中，阻挡层411可以是由金属介电层(诸如根据需要是Ta2O5或TiO2或任何合适的金属介电层)制造的单层的含金属介电层，如图4中所描绘的。在另一个实施方式中，阻挡层411可以根据需要呈现复合膜的形式。
栅极电极层414形成于栅极绝缘层406的顶部上，其中阻挡层411介于二者之间。栅极绝缘层406通常也称为栅极氧化物层，因为它通常是由二氧化硅(SiO2)层制成的。绝缘材料层412(诸如层间绝缘体)和装置连接件(未示出)接着被制造为通过绝缘材料层412以允许控制TFT装置。
在绝缘材料层412形成之后，源极-漏极金属电极层410a、410b接着被沉积、形成、和图案化在绝缘材料层412中。在源极-漏极金属电极层410a、410b被图案化之后，钝化层418接着被形成在源极-漏极金属电极层410a、410b上方。
图5描绘分别在含金属层(诸如分别在图3-4中的有源层306、452、或分别在图3-4中的金属电极302、310、410a、410b、414)上执行的热退火处理500的一个实例的流程图。
方法500藉由提供基板(诸如图3和4中的基板301)开始于操作502处。基板301可以是光学透明基板。基板301可包括设置在其上的材料层601，如图6A中所示。材料层601可以是可以用来形成TFT装置结构的单个层或多个层。或者，材料层601可以是可包括可以用来形成TFT装置结构的多种材料的结构。
基板301进一步包括形成于材料层601上的含金属层602，如图6B中所示。在不存在材料层601的实例中，可以将含金属层602直接形成于基板301上。在一些实例中，可以将含金属层602用作图3或4中的有源层306、452、或图3-4中的金属电极302、310、410a、410b、414。在一个实例中，含金属层602是选自由以下各者构成的组的金属氧化物层：a-IGZO(非晶铟镓锌氧化物)、掺杂的IGZO、InGaZnON、ZnO、ZnON、ZnSnO、CdSnO、GaSnO、TiSnO、CuBO2、CuAlO2、CuGaO2、SrCuO、LaCuOS、GaN、InGaN、AlGaN、或InGaAlN和类似者。在一个实例中，含金属层602是IGZO或掺杂的IGZO层。或者，含金属层602可以是金属层，诸如铜(Cu)、金、银(Ag)、铝(Al)、钨(W)、钼(Mo)、铬(Cr)、钽(Ta)、上述各者的合金或类似者。
在操作504处，执行可选的离子掺杂/注入处理以将离子注入到含金属层602中，而形成掺杂的含金属层610，如图6C中所示。在离子注入处理被消除的实例中，可以直接在含金属层602上执行操作506处的热退火处理(下文将更详细地描述)。离子掺杂/注入处理被执行为在含金属层602的某些位置上进行掺杂、涂覆、处理、注入、安插、或更改某些膜/表面性质，其中掺杂物形成于所述含金属层中而形成掺杂的含金属层610。离子掺杂/注入处理利用入射的离子来更改含金属层602上的膜/表面性质，其中掺杂物被掺杂到所述含金属层中以形成掺杂的含金属层610。可以在任何合适的离子注入/掺杂处理工具中执行离子掺杂/注入处理。可以用所需的浓度将包括所需类型的原子的离子掺杂到含金属层602中。掺杂到含金属层602中的离子可以更改含金属层602的膜/表面性质，这可以影响、改善、或变更含金属层602的晶格结构、结晶度、键合结构、或膜密度，从而形成掺杂的含金属层610。
在含金属层602包括InGaZnO的实施方式中，掺杂到含金属层602中的离子可包括铟(In)或钼(Mo)、镓(Ga)、锌(Zn)和类似者。据信，掺杂到含金属层602(例如InGaZnO)中的In或Mo掺杂物可以变更InGaZnO材料的电气性质，例如高迁移率、结晶度(例如来自非晶结构、C轴取向的晶体结构(CAAC)、多晶结构、或甚至单晶结构)，因此提供了具有所需膜性质的掺杂的含金属层610。例如，由InGaZnO材料中的In或Mo掺杂物所提供的较高程度的结晶度据信增加了膜性质的电子迁移率，因此在TFT装置结构或半导体装置中利用掺杂的含金属层610时增强了TFT装置结构或半导体装置的电气性能。
并且，也据信，包括在InGaZnO材料中的镓(Ga)和氧化锌(ZnO)比率也可以影响掺杂的含金属层610的生成的晶格结构。据信，包括在InGaZnO材料中的Ga元素的比率可以增加膜透明度以及整体的膜带隙。包括在InGaZnO材料中的Zn或ZnO元素的比率可以增加迁移率以及降低增强结晶度的热退火温度需求。因此，藉由选定掺杂到InGaZnO材料中的适当剂量的In掺杂物，可以获得所需的InGaZnO材料晶体。并且，所需的InGaZnO材料晶体也可以帮助降低之后的操作506处的热退火处理中的温度需求，从而在TFT装置应用中提供了处理优势，因为基板301通常是具有相对较低的热循环预算的光学透明材料。
在一个实施方式中，InGaZnO材料中的生成的In掺杂物可具有形成于掺杂的含金属层610中的在约5E15离子数/cm2至约9E15离子数/cm2之间(诸如约8.5E15离子数/cm2)的掺杂浓度。并且，可以将InGaZnO材料中的In或Mo元素的用原子量(atomic weight)计的比率从约10％-13％增加到约14％-16％(在约15％和约30％之间的增加)。
可以在离子掺杂/注入处理期间控制几个处理参数。可以藉由以下步骤来执行离子掺杂/注入处理：将离子掺杂气体混合物以及所需量的功率能量供应到离子掺杂/注入工具中，以将来自离子掺杂气体混合物的离子掺杂到基板301中。可以用在约10sccm和约1000sccm之间的流量(flow rate)将离子掺杂气体混合物供应到离子掺杂/注入工具中。用于在注入期间在所使用的离子掺杂操作中用气态供应的合适元素包括铟蒸气和钼蒸气。可以将RF功率(诸如电容式或感应式RF功率)、DC功率、电磁能、离子束、或磁控溅射供应到离子掺杂/注入处理中以协助在处理期间解离离子掺杂气体混合物。可以使用藉由向基板支撑件、或向基板支撑件上方的气体入口、或向所述基板支撑件和所述气体入口二者施加DC或RF电偏压产生的电场将由解离能所产生的离子朝向基板加速。在一些实施方式中，含气体的高能离子可以是等离子体。可以使用在约20keV和约80keV之间(诸如在约35keV和约55keV之间，例如约45keV)的能量来将离子注入到含金属层602中。可以将基板温度控制在约5摄氏度和约50摄氏度之间，诸如约15摄氏度。
在操作506处，执行高压退火处理。在高处理压力(诸如大于2巴但小于)下执行的退火处理可以协助致密化和修复掺杂的含金属层610中的空位(vacancies)，从而形成具有所需的膜性质的退火的含金属层603，如图6D中所示。在一些实例中，高的处理压力可以高达100巴。在不执行操作504处的离子掺杂/注入处理的实施方式中，可以直接在来自图6B的含金属层602上执行高压退火处理以形成退火的含金属层603，如图6D中所示。可以在处理腔室(诸如图1中所描绘的处理腔室100)或其他合适的处理腔室(包括一次处理一个基板的那些处理腔室)处执行退火处理。
在操作506处执行的高压退火处理将高压区域处的处理压力维持在气相(例如实质上不存在液滴的干气相)下。处理压力及温度被控制为致密化膜结构，以便修复膜缺陷，从而驱除杂质和增加膜密度。在一个实例中，高压区域115被加压到大于大气的压力，例如大于约2巴。在另一个实例中，高压区域115被加压到从约5巴到约100巴的压力，诸如从约5巴到约50巴，诸如约35巴。因为高压可以高效地协助致密化膜结构，相对较低的处理温度(诸如小于500摄氏度)减小了热循环损坏基板301的可能性。
在处理期间，高压区域115被设置在外腔室110内的加热器122维持在相对较低的温度下，例如小于500摄氏度的温度，诸如在约150摄氏度和约350摄氏度之间。因此，可以藉由利用高压退火处理以及低温方案来获得低的基板热预算。
据信，高压处理可以提供驱动力以驱除含金属层602或掺杂的含金属层610中的悬键(dangling bond)，因此在退火处理期间使含金属层602中的悬键修复、反应、和饱和。在一个实例中，可以在退火处理期间供应含氧气体(诸如O3气体、O2气体、空气、H2O、H2O2、N2O、NO2、CO2、CO、和干蒸气)、或硫族蒸气(包括硫(S)蒸气和硒(Se)蒸气)、或碲蒸气、或其他合适的气体。在一个具体实例中，含氧气体包括蒸气，例如干蒸气和/或空气。可以将在退火处理期间来自含氧气体的氧元素驱动到含金属层602中，从而变更其中的键合结构和移除原子空位，因此致密化和增强了含金属层602的晶格结构以及增加了所述含金属层的结晶度。在一些实例中，可以与含氧气体一起供应惰性气体或载气(诸如Ar、N2、He、Kr和类似者)。在一个实施方式中，在含氧气体混合物中供应的含氧气体是在大于2巴的压力下供应的干蒸气。
在一个示例性的实施方式中，处理压力被调节在大于2巴的压力下，诸如在5巴和100巴之间，诸如在20巴和约80巴之间，例如在约25巴和75巴之间，诸如约35巴。可以将处理温度控制在大于150摄氏度但小于500摄氏度，诸如在约150摄氏度和约380摄氏度之间，诸如在约180摄氏度和约400摄氏度之间。在一个实例中，可以在用于金属氧硫族元素(诸如包括S或Se的InGaZnO)的退火处理期间供应硫族蒸气(诸如硫(S)蒸气、硒(Se)蒸气)。
在高压下的退火处理之后，与通过一个大气压力左右的压力下的传统退火处理来退火的含金属层602或掺杂的含金属层610相比，含金属层602或掺杂的含金属层610具有致密化的膜结构，这提供了具有非晶形态的相对稳健(robust)的膜结构，所述膜结构提供了更高的膜密度、高的膜迁移率、低的载体浓度、和低的膜电阻率，其中两种退火处理都处于相同的退火温度下。在一个实例中，与1大气压力下且相同退火温度下的传统退火处理相比，具有铟掺杂物的高压退火的含金属层603(由掺杂的含金属层610所形成)的迁移率增加了约5倍和约20倍之间，电阻率增加了约10倍，且载体浓度减小了约100倍。
在一个实例中，与1大气压力下且相同退火温度下的传统退火处理相比，不具有铟掺杂物的高压退火的含金属层603(由含金属层602所形成)的迁移率增加了约1.5倍和约5倍之间，电阻率增加了约20百分比至约99百分比，且载体浓度减小了约100倍。
因此，提供了用于热退火含金属层的方法。可以通过具有高处理压力(诸如大于2巴但小于50巴)的高压退火处理来热处理/退火含金属层。通过利用此类高压退火处理，可以将处理温度维持在小于500摄氏度，因此减小了贡献给其上形成有含金属层的基板的热预算，从而提供了具有所需的结晶度及结构集成管理的良好膜品质。
尽管上文是针对本发明的实施方式，但是可以在不背离本发明的基本范围的情况下，设计出本发明的其他的和进一步的实施方式，且本发明的范围是由随附的权利要求书来确定的。

Claims (15)

1.一种在基板上形成含金属层的方法，所述方法包括以下步骤：
在处理腔室中的基板上供应含氧气体混合物，所述基板包括设置在光学透明基板上的含金属层；
将所述处理腔室中的所述含氧气体混合物维持在2巴和50巴之间的处理压力下；和
在所述含氧气体混合物存在的情况下热退火所述含金属层。
2.如权利要求1所述的方法，其中供应所述含氧气体混合物的步骤进一步包括以下步骤：
将基板温度维持在小于400摄氏度。
3.如权利要求1所述的方法，其中含氧气体混合物至少包括选自由以下各者构成的组中的含氧气体：O3气体、O2气体、H2O、H2O2、N2O、NO2、CO2、CO、空气、干蒸气。
4.如权利要求1所述的方法，其中含氧气体混合物包括干蒸气或空气。
5.如权利要求1所述的方法，其中所述处理压力是在约5巴和100巴之间。
6.如权利要求1所述的方法，其中所述含金属层是金属氧化物层。
7.如权利要求1所述的方法，其中所述金属氧化物层选自由以下各者构成的组：a-IGZO(非晶铟镓锌氧化物)、掺杂的IGZO、InGaZnON、ZnO、ZnON、ZnSnO、CdSnO、GaSnO、TiSnO、CuBO2、CuAlO2、CuGaO2、SrCuO、LaCuOS、GaN、InGaN、AlGaN、和InGaAlN。
8.如权利要求1所述的方法，进一步包括以下步骤：
在供应所述含氧气体混合物之前将掺杂物注入到所述含金属层中。
9.如权利要求8所述的方法，其中注入到所述含金属层中的所述掺杂物包括铟或钼。
10.如权利要求9所述的方法，其中注入到所述含金属层中的所述掺杂物增加了所述含金属层的结晶度。
11.如权利要求1所述的方法，其中所述含金属层是TFT装置结构中的有源层。
12.如权利要求1所述的方法，其中所述金属氧化物层是InGaZnON。
13.如权利要求1所述的方法，其中所述含金属层是TFT装置结构中的电极。
14.如权利要求1所述的方法，其中所述含金属层在所述热退火步骤之后具有较高的迁移率。
15.如权利要求1所述的方法，其中所述含金属层在所述热退火步骤之后具有较高的膜密度。
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