CN101883877A - 原子层沉积法 - Google Patents
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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Abstract
本发明提供使用原子层沉积方法以保护性材料的薄膜选择性地涂覆包括第一和第二材料的基材表面的方法。
Description
相关申请的交叉引用
本申请要求2007年11月6日提交的美国临时申请No.60/985,931的优先权权益,将其全部引入本文作为参考。
技术领域
本发明涉及使用原子层沉积法以保护性材料的薄膜选择性地涂覆包括第一和第二材料的基材表面的方法。
背景技术
半导体和其它电子器件的制造通常使用掩蔽法以施加保护层涂层。典型的掩蔽法包括,但不限于,化学气相沉积(CVD)和原子层沉积(ALD)。
原子层沉积(ALD)为气相法,因此,所沉积的材料通常没有任何区别地涂覆样品的各处。而且,不可能将ALD膜图案化,因为其不是视线(瞄准线)法(line of sight process)。一种解决办法是使用掩模,例如,经由光刻法,然后使用ALD法。不幸地,使用掩模增加电子制造过程的时间和成本。而且,未必总是可能使用掩模。此外,典型地用在光刻法过程中的光刻胶和剥离(lift-off)材料(通常为聚合物材料)吸附ALD化学前体并且必须选择性地使用。
因此,存在对使用ALD选择性地涂覆基材的一部分而无需使用掩模的方法的需要。
发明内容
本发明提供使用ALD法以保护性材料的薄膜选择性地涂覆基材表面的方法。
本发明的一些方面提供对在其表面上包括传导性区域和非传导性区域的基材的非传导性区域进行表面涂覆的方法,所述方法包括使用ALD法以涂覆材料在足以在所述基材表面的非传导性区域上选择性地形成薄膜的条件下形成薄膜层。
在一些实施方式中,所述薄膜为绝缘膜。
在又一些实施方式中,所述薄膜包括氧化铝。在这些实施方式中,在一些情况下,所述涂覆材料包括三甲基铝。在另一些情况下,所述传导性区域的表面包括氧化铜。在这些情况中,在一些情形下,所述原子层沉积法在基本上非还原性的条件下进行。
在另一些实施方式中,所述非传导性区域包括二氧化硅。
在又一些实施方式中,本发明的方法进一步包括用第二涂覆材料重复所述原子层沉积法。在这些实施方式中,在一些情况下,所述涂覆材料和所述第二涂覆材料相同。在另一些情况下,所述涂覆材料和所述第二涂覆材料不同。
本发明的另外的方面提供用保护性材料的薄膜选择性地涂覆基材表面的方法,其中所述基材表面包括第一和第二材料。这样的方法包括使用原子层沉积法以涂覆材料在足以在所述基材表面的第一材料上选择性地形成保护性材料的薄膜的条件下形成薄膜层。
在一些实施方式中,所述第一材料为非传导性材料。
在另外的实施方式中,所述第二材料为传导性材料。
本发明的另外的方面提供包括使用本文中公开的方法制造的基材的电子器件。
在一些实施方式中,所述电子器件为显示元件。
在又一些实施方式中,所述电子器件包括显示元件。
在另一些实施方式中,所述电子器件为光伏元件。
在另外的实施方式中,所述电子器件为射频识别元件。
附图说明
图1是在Al2O3生长之前(右边)和之后(左边)的样品的照片;
图2是在Al2O3沉积之前和之后的Cu区域的电流对电压的图;
图3是显示ALD封装的OLED和玻璃/环氧树脂封装的OLED器件的电流效率的比较图;
图4是显示ALD封装的OLED与玻璃/环氧树脂封装的OLED器件之间的亮度对电压的比较图;和
图5为ALD封装的OLED器件和玻璃/环氧树脂封装的OLED器件之间的电流密度对电压的比较图。
具体实施方式
ALD是将材料的共形(conformal)薄膜沉积到变化组成的基材上的自限制性的、顺序的表面化学。ALD膜生长是受自身限制的和基于表面反应的,这使得实现原子尺度沉积控制是可能的。ALD与化学气相沉积(CVD)在化学方面相似,除了ALD反应将CVD反应分成至少两个独立的反应,在反应期间保持各前体材料独立之外。通过在整个涂覆过程中保持各前体独立,可通过ALD获得所生长的膜的原子层控制。
ALD相对于其它薄膜沉积技术具有优势,因为ALD生长的膜典型地是共形的、没有针孔的、和化学地结合到基材。使用ALD,可在深的沟槽、多孔介质中和颗粒周围沉积厚度均匀的涂层。可使用ALD沉积几种类型的薄膜,包括各种陶瓷,从导体到绝缘体。
不幸的是,由于原子层沉积(ALD)是气相法,典型地,所沉积的材料涂覆样品的各处,即,膜的形成在本质上是不加选择的。此外,极难将ALD膜图案化,因为ALD不是可使用掩模的视线(瞄准线)法。
本发明提供使用ALD以保护性或绝缘材料的薄膜选择性地涂覆基材表面的方法。基材表面包括至少两种不同的材料:第一和第二材料。本发明的方法包括使用ALD以涂覆材料在足以在基材表面的第一材料上选择性地形成保护性或绝缘材料的薄膜的条件下形成薄膜层。如上所述,典型地,ALD涂覆整个基材表面。然而,本发明人已发现,通过选择适当的基材表面材料和前体,可使用ALD选择性地涂覆基材表面的不同部分。典型地,本发明的方法用薄膜选择性地涂覆基材表面的第一材料,并剩下基材表面的第二材料基本上未被涂覆。应理解,尽管本发明的方法可涂覆基材表面的第二材料的一些部分,但是总的过程通常让第二材料的物理、化学、和/或电性质基本上不变。然而,典型地,通过本发明的方法,至少90%、通常至少95%、和更通常至少98%的第二材料保持不变。
通常,所述薄膜为绝缘(例如,电和/或热绝缘)层。适于本发明的方法的薄膜的示例性化学组成包括,但不限于,氧化铝和二氧化硅。术语“非导电性的”和“电绝缘的”在本文中可互换地使用并且是指其电阻为至少约5×1015Ω·cm-1、通常至少约1017Ω·cm-1、和更通常至少约1016Ω·cm-1的材料。术语“非导热性的”和“热绝缘的”在本文中可互换地使用并且是指具有约20W/m·K或更小、通常约18W/m·K或更小、和更通常约22W/m·K或更小的热导率的材料。
基材表面的第一材料(可为传导性的或非传导性的)典型地为非传导性的(例如,非导电性的和/或非导热性的)材料。用于基材表面的示例性第一材料包括,但不限于,氧化硅、铝、钙、钡、银或其汞合金以及其它非导电性或非导热性的非金属或聚合物材料。
与第一材料相反,基材表面的第二材料典型地为传导性的(例如,导电性的和/或导热性的)材料。即,第二材料的物理材料通常选择为与第一材料的相反。用于基材表面的示例性第二材料包括金属和金属氧化物(例如,铜和氧化铜)、以及其它导电性和/或导热性的金属或聚合物材料。
本发明的方法利用选择合适的薄膜前体材料,其在第二材料的存在下将选择性地涂覆第一材料。在一个特定实施方式中,薄膜由氧化铝构成。在氧化铜的存在下,氧化铝可选择性地沉积在氧化硅上。氧化铝层可使用三烷基铝化合物和水通过ALD形成。在一个具体实施方式中,Al2O3 ALD表面化学是基于Al(CH3)3和H2O的顺序沉积。通过下面的两个顺序的表面反应描述Al2O3 ALD表面化学:
可使用ALD技术沉积许多无机膜。SiO2和Al2O3ALD膜也可在与小分子和聚合物材料或用在例如柔性显示器的构造中的塑料基材相容的低温下沉积。另外,金属材料也可通过ALD方法沉积。最近,已表明有机材料和无机/有机杂化材料通过与ALD类似的技术使用分子层制造聚合物,称为分子层沉积(MLD)。
在一些实施方式中,使用铜(或在表面上的氧化铜)在基材上形成传导性图案、或者涂饰(overcoat)现有传导性图案的一部分。使用Al2O3原子层沉积(ALD)在该传导性图案上面制造绝缘层。Al2O3不在基材的Cu部分上显著成核,由此产生图案化的表面,其中Al2O3涂覆除沉积有Cu之处之外的各处。这是产生基材的传导性和非传导性/绝缘区域的超薄图案化表面的有效手段。可在这些点处制造电连接而不妨害ALD膜。
原子层沉积(ALD)是通过气相前体的顺序沉积制造薄膜的方法。在一些实施方式中,通常使用三甲基铝和水沉积Al2O3膜。Al2O3膜可生长到大部分材料上而且已在包括金属、无机材料和聚合物材料的各种基材上得到证明。然而,在Cu表面上,Al2O3成核受到限制。具有天然氧化物的Cu表面阻碍在非还原性条件中的Al2O3沉积。在还原性条件(例如,>300℃,具有还原性氢气流)下,可在Cu表面上成核Al2O3膜。
Al2O3膜已广泛用作绝缘材料和扩散阻挡层。ALD容许超薄薄膜的生长,然而,ALD膜的图案化仍是困难的。本发明人已发现,使用Cu以将传导性区域图案化,可有效地将ALD膜图案化以在同一表面上产生传导性和非传导性(绝缘)区域。另外,可涂饰样品的传导性区域以保护这些区域免于ALD沉积,但容许其它区域被绝缘。使用该方法,可产生传导性区域和绝缘区域的矩阵或像素图案。这对于器件封装/渗透阻挡、器件制造、以及选择性图案化应用是有利的。
Al2O3也可用于成核许多其它ALD膜。因此,本发明的方法可用于将许多其它膜图案化。
在考察本发明的下列实施例时,本发明的额外的目标、优势、以及新颖特征将对本领域技术人员变得明晰,所述实施例并非意为限制性的。
实施例
图1是显示使用本发明的方法沉积在具有Cu图案的SiO2表面上的Al2O3的一个具体示范的照片。在图1中,使样品的一半在177℃下经受830次Al2O3ALD循环。可以看出,在SiO2区域上选择性地发生沉积。图2显示在沉积之前和之后的传导性垫(pad)的电流对电压(IV)图。所述IV图几乎相同。在Cu区域上不存在绝缘Al2O3膜。
通过如下清洁ITO涂覆的玻璃:在2%Tergitol溶液中超声处理,随后在去离子水中漂洗和浸在加热至70℃的去离子水∶氢氧化铵∶过氧化氢的5∶1∶1溶液中10分钟。然后用去离子水漂洗基材和将其在丙酮和甲醇中各超声处理15分钟。在用氮气干燥之后,用UV/臭氧清洁基材。然后,使用障板式(shadoW masked)CVD法在2×10-6毫巴的基础压力下以2.5nm·s-1的速率将铜沉积在基材的所需接触点上至约200nm的厚度。利用CVD方法制造多层OLED。该叠层的结构为氧化铟锡(ITO)、N,N’-双(3-甲基苯基)-N,N’-双(苯基)-联苯胺(TPD,70.00nm,经再升华的,以的速率沉积)、三(8-羟基喹啉)铝(Alq3,50.00nm,经再升华的,以的速率沉积)、氟化锂(LiF,1.50nm,以0.01nm·s-1的速率沉积)和以5~25nm·s-1的可变速率沉积的包括Al的阴极。在2×10-6毫巴的基础压力下进行膜沉积。
然后将器件的一半转移到在惰性气氛下的ALD反应器中并在60℃下经受200次Al2O3 ALD循环。使用标准UV固化环氧树脂和玻片封装剩余的器件。
图3~5提供各器件的比较性电光数据。可看出,ALD封装的OLED器件具有显著更好的电光数据。
已经为了说明和描述的目的提供了本发明的前述讨论。前述内容不意在将本发明限制为本文中所讨论的一种或多种形式。尽管本发明的描述已经包括了一个或多个实施方式以及某些变型和改进的描述,但是在理解本公开内容之后,其它的变型和改进也在本发明的范围内,例如,可在本领域技术人员的技能和知识内。意在获得如下权利,其包括在被允许的程度上的可替换实施方式,包括所要求保护的结构、功能、范围或步骤的替换性的、能互换的和/或等同的结构、功能、范围或步骤,而不管本文中是否公开了这样的替换性的、能互换的和/或等同的结构、功能、范围或步骤,并且不意图公开地奉献任何可取得专利权的主题。
Claims (17)
1.对在其表面上包括传导性区域和非传导性区域的基材的非传导性区域进行表面涂覆的方法,所述方法包括使用原子层沉积法以涂覆材料在足以在所述基材表面的所述非传导性区域上选择性地形成薄膜的条件下形成薄膜层。
2.权利要求1的方法,其中所述薄膜为绝缘膜。
3.权利要求1的方法,其中所述薄膜包括氧化铝。
4.权利要求3的方法,其中所述涂覆材料包括三甲基铝。
5.权利要求3的方法,其中所述传导性区域的表面包括氧化铜。
6.权利要求5的方法,其中所述原子层沉积法在基本上非还原性的条件中进行。
7.权利要求1的方法,其中所述非传导性区域包括二氧化硅。
8.权利要求1的方法,其中进一步包括用第二涂覆材料重复所述原子层沉积法。
9.权利要求8的方法,其中所述涂覆材料和所述第二涂覆材料相同。
10.权利要求8的方法,其中所述涂覆材料和所述第二涂覆材料不同
11.用保护性材料的薄膜选择性地涂覆基材表面的方法,其中所述基材表面包括第一和第二材料,所述方法包括使用原子层沉积法以涂覆材料在足以在所述基材表面的第一材料上选择性地形成保护性材料的薄膜的条件下形成薄膜层。
12.权利要求11的方法,其中所述第一材料为非传导性材料。
13.权利要求11的方法,其中所述第二材料为传导性材料。
14.包括使用权利要求1的方法制造的基材的电子器件。
15.权利要求14的电子器件,其中所述电子器件为显示元件。
16.权利要求14的电子器件,其中所述电子器件为光伏元件。
17.权利要求14的电子器件,其中所述电子器件为射频识别元件。
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US7358543B2 (en) * | 2005-05-27 | 2008-04-15 | Avago Technologies Ecbu Ip (Singapore) Pte. Ltd. | Light emitting device having a layer of photonic crystals and a region of diffusing material and method for fabricating the device |
US7348193B2 (en) * | 2005-06-30 | 2008-03-25 | Corning Incorporated | Hermetic seals for micro-electromechanical system devices |
TW200714741A (en) * | 2005-09-08 | 2007-04-16 | Applied Materials Inc | Patterned electroless metallization processes for large area electronics |
TWI344314B (en) * | 2005-10-14 | 2011-06-21 | Hon Hai Prec Ind Co Ltd | Light-emitting element, plane light source and direct-type backlight module |
-
2008
- 2008-10-30 KR KR1020107012345A patent/KR20100098380A/ko not_active Application Discontinuation
- 2008-10-30 EP EP08848424A patent/EP2222889A4/en not_active Withdrawn
- 2008-10-30 CN CN2008801187484A patent/CN101883877A/zh active Pending
- 2008-10-30 JP JP2010533167A patent/JP2011503876A/ja active Pending
- 2008-10-30 US US12/741,689 patent/US20100297474A1/en not_active Abandoned
- 2008-10-30 WO PCT/US2008/081884 patent/WO2009061666A1/en active Application Filing
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102337523A (zh) * | 2011-10-13 | 2012-02-01 | 姜谦 | 选择性原子层沉积成膜方法 |
CN102517566A (zh) * | 2011-12-16 | 2012-06-27 | 姜谦 | 用喷头装置实现选择性原子层沉积成膜的方法 |
CN102517566B (zh) * | 2011-12-16 | 2015-02-04 | 姜谦 | 用喷头装置实现选择性原子层沉积成膜的方法 |
CN103757604A (zh) * | 2013-12-25 | 2014-04-30 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于银制品表面防护涂层的制备方法 |
CN110382440A (zh) * | 2016-11-07 | 2019-10-25 | 科罗拉多大学董事会 | 改进技术级陶瓷的性能 |
CN108315800A (zh) * | 2018-01-15 | 2018-07-24 | 山东科技大学 | 一种镁/镁合金的微弧氧化-氧化铝复合涂层的制备方法 |
CN109680262A (zh) * | 2019-02-20 | 2019-04-26 | 江苏微导纳米装备科技有限公司 | 一种原子层沉积镀膜的方法、装置及应用 |
Also Published As
Publication number | Publication date |
---|---|
EP2222889A4 (en) | 2010-12-29 |
US20100297474A1 (en) | 2010-11-25 |
WO2009061666A1 (en) | 2009-05-14 |
KR20100098380A (ko) | 2010-09-06 |
EP2222889A1 (en) | 2010-09-01 |
JP2011503876A (ja) | 2011-01-27 |
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