CN100575536C - 用于蒸发锂的混合物 - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000001704 evaporation Methods 0.000 title claims abstract description 29
- 230000008020 evaporation Effects 0.000 title claims abstract description 29
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- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明描述了锂盐与还原剂的混合物用于锂蒸发的用途，尤其是用于制备有机电致发光显示器。也描述了基于使用这些混合物的锂分配器。
Description
本发明涉及在工业应用中用于锂蒸发的混合物，以及使用这些混合物的锂分配器，其中在所述工业应用中需要该混合物。
锂长期以来用于电子领域。特别地，这种金属在过去已用于生产光敏表面，如图像放大器或光-倍增管。合金或盐形式的锂的另一重要用途是用于生产电池元件。
锂的新应用领域在OLED(“有机发光显示器”)屏幕中。由于这种应用的重要性，下面将特别地参照这一点，但是本发明具有更广泛的适用性。
简单地说，OLED是由下列元件形成的：第一平面透明载体(由玻璃或塑料制成)；第二载体，不必要是透明的，其可以形成于玻璃、金属或塑料中，基本上是平面的且平行于第一载体和沿其周边固定，由此形成封闭空间；和用于在所述空间中形成图像的活性结构。反过来，该活性结构是由下列元件形成的：第一组透明、线性且互相平行的电极，通常具有阳极功能，沉积在第一载体之上；沉积在第一组电极之上的不同电致发光有机材料的多个层，包括至少一个电子导体材料的层和至少一个空穴导体材料的层；第二组线性且互相平行的电极，其相对于第一组电极正交取向且具有阴极功能，与多层有机材料的对侧相接触，使得后者包含在两组电极之间。对于OLED屏幕的结构和操作原理的更详细解释，可以参照例如专利申请EP-A-845924、EP-A-949696、JP-A-9-078058和专利US 6,013,384。
最近已发现，将少量电子给体材料加入到OLED结构中，能使得施加到两组电极上用于运行该屏幕的电压差降低，并且由此降低其能耗。特别地，US专利6,013,384公开了使用一些金属来掺杂有机多层的一个或多个层，同时US专利6,255,774公开了在阴极和相邻有机层之间形成非常薄的层(小于5nm)。阅读这两篇专利(特别是从实施例中)可以清楚地看出，特别适用于该目的的元素为锂，可能是因为其小尺寸使得能生成特别薄的、连续的层或能使其分散于有机基质中。
由于对空气和湿度的高反应性，锂(类似于任意碱金属)工业上通常不能以纯金属形式来使用，而是以室温下在空气中稳定的化合物形式来使用。最通常使用的化合物为与还原剂的掺混物中的重铬酸盐Li2Cr2O7、或更普遍的铬酸盐Li2CrO4。通过在通常高于500℃的温度下加热这些混合物，发生反应，由此将铬还原为较低化合价，结果将锂作为蒸气释放出来。作为还原剂，通常使用铝、硅或吸气合金(即与铝或一种或多种过渡元素的钛-或锆基合金)。这些混合物的使用例如公开于专利US 2,117,735和US 3,578,834。该混合物体通常用在能够保持固体颗粒的适宜分配器之内，但是该分配器的至少一部分表面能使碱金属蒸气透过，如例如专利US 3,579,459和US 4,233,936中所示的那些。
但是，碱金属的铬酸盐和重铬酸盐所存在的缺陷是，含有六价的铬，其可以通过接触、吸收或吸入而引起刺激，并且在长时间暴露时可能致癌。
为了避免使用铬酸盐，已提出利用锂的合金例如与铝的合金。使用这种合金的实例公开于文献：F.J.Esposto等，出版于J.Vac.Sci.Technol.，第3245-7页，第12卷第6期，1994的“Simple source ofLi metal for evaporators in ultrahigh vacuum(UHV)applications”。类似申请的另一实例公开于日本专利申请公报JP2004-164992。但是，采用这些合金是有问题的，由于它们的锂蒸发性能非常不规则，同时存在金属的突然排出，导致它们基本上不可用于工业生产。
国际专利申请公报WO 2004/066337 A1、WO 2004/066338 A1和WO 2004/066339 A1分别描述了使用碱金属的钨酸盐、钼酸盐和钒酸盐来释放碱金属，但是并没有具体描述或提及锂盐。
本发明的目的是提供用于锂蒸发的混合物，其克服了现有技术的问题。
本发明的另一目的是提供利用这些混合物的锂分配器。
通过本发明处理锂盐和还原剂之间的混合物的方式，实现了这些和其它目的，其特征在于锂盐选自钛酸盐(Li2TiO3)、钽酸盐(LiTaO3)、铌酸盐(LiNbO3)、钨酸盐(Li2WO4)和锆酸盐(Li2ZrO3)。
下面将参照附图来描述本发明，其中：
-图1显示了依据本发明的可能的锂分配器的透视图、部分切掉的截面；
-图2显示了依据本发明的锂分配器的优选形式的透视图、部分切掉的截面；和
-图3显示了表示使用本发明混合物的分配器的锂蒸发性能的图表。
本发明人已发现，一种或多种还原剂与选自于上述那些的锂盐的混合物，不仅消除了借助于六价铬的化合物的必要性，而且也具有赋予它们有益的工业利用的额外性能。首先，锂蒸发的特征(尤其是速率)可以容易地得到控制且是可再现的。另外，所述锂盐比铬酸盐吸湿性低很多，由此降低了锂蒸发期间也可能蒸发湿气的风险，其对于OLED运行来说是极端危险的。所述盐之中，优选钛酸盐，因为其具有最高的锂重量百分含量，而且也因为在本发明人进行的试验中已发现这种盐对于其蒸发需要最小的能量数值；另外，已发现钛酸锂能带来特别平稳的锂蒸发，因此容易控制。
US专利6,753,648 B2(以本申请人的名义)描述了与本发明那些盐类似的盐，用于蒸发铯。但是，由于锂和铯之间化学特性的差别(由于离子Li+相对于Cs+具有特别小的尺寸和高的极化性)，所引用的US专利的教导并不能直接应用于锂情形中；例如钼酸阴离子与铯形成适用于蒸发碱金属的盐，但是其与锂形成的盐会导致突然的和不可控的蒸发，不适用于工业应用；相反，实际上钛酸铯是无用的，因为其吸湿性过大，但是钛酸锂证实是用于锂蒸发的优选盐。
用于本发明混合物中的还原剂可以是一种用于基于铬酸盐的分配器中的已知组分，例如铝、硅、锆或钛，或含有锆或钛的合金，如重量百分比组成为Zr 84％-Al 16％的合金(其由申请人生产并以牌号St
销售)，或重量百分比组成为Zr 76.5％-Fe 23.5％的合金(其由申请人生产并以牌号St
销售)。也可以使用多种还原剂的混合物。
为了增强锂化合物与还原剂之间的接触，优选以粉末形式来使用。两种混合物组分的粒径通常小于1mm且优选小于500μm；仍更优选地粒径包含在约10-125μm之间。粒径小于10μm的粉末通常在生产时难以处理，和难以保持在分配器之内；另外，在还原剂情形中，过细的粉末可以变为自燃的，带来生产设备中的安全问题。相反，使用粒径大于所述值的粉末时，混合物的两种组分之间的接触变得较差，并且导致产生锂蒸发的反应减慢。
锂盐和还原剂之间的重量比可以在宽范围内变化。优选地，该比例包含为10∶1-1∶10。使用相对于还原剂大量过量的锂盐无实际优点；反之亦然，尤其是当还原剂为吸气合金如所述St合金时，混合物中其过量可能是有益的，因为不参予与锂盐的反应的那部分可以具有吸附反应期间可能被释放的气体的效果。锂盐与还原剂的优选重量比为1∶5。
该混合物可以以疏松粉末形式来使用。但是，优选以粒料形式来使用，其具有的优点是，进一步改进了混合物组分之间的接触并且有利于装填容器的操作。本发明人已发现，粒料相对于粉末的另一优点是，粒料需要较少量用于锂蒸发的能量，并且更彻底地使用该混合物的锂装载量，在实施例部分通过试验更详细地描述这点。
该容器可以是在适用于本发明的任意材料中制成和制成任意形状。
特别地，至于所涉及的材料，其在使用中预见到的任意温度(其可以超过1000℃)下对处理气氛和锂分配混合物应当是化学惰性的；另外，在使用温度下，形成该容器的材料应当不存在实质的物理变化，以至于保持其机械强度或形状，并且必须具有尽可能低的透气值。具有这些特征的材料例如为金属或金属合金、一些陶瓷或石墨。优选采用金属和合金，因为它们容易加工和成型。使用金属和合金的另一优点是，可以简单地通过使气流流过容器壁来使分配器在锂蒸发温度下加热。用于制备该容器的优选金属和合金为钼、钽、钨、镍、钢和镍-铬或镍-铬-铁合金。
该容器的形状可以是专利US 3,578,834、US 3,579,459、US3,598,384、US 3,636,302、US 3,663,121、US 4,233,936和US6,753,648B2中公知的那些中的任意形状。各种形状和材料的容器也可以在商业上获得，例如从澳大利亚公司Plansee或美国公司MidwestTungsten Service获得。本发明分配器的一种可能形状如图1中所示。分配器10由内部具有本发明混合物的容器组成。该容器由顶部部件11和底部部件12的组件形成；两个部件优选由金属制成，并且例如通过点焊将其彼此相连。底部部件在其中心区域中具有凹槽(例如通过冷冲压获得)，其中装有本发明的混合物，同时上部部件具有多个开口13、13′...，以能使得排出锂蒸气；其位于由虚线所定义的、对应于部件12中凹槽的部件11的划线区域中。如图中所示，本发明的混合物可以以粉末形式存在于部件12的凹槽中，其中混合物表述为元素14；替换地，可以形成混合物的粒料并用其填充凹槽。分配器10在其两端具有“翼”15和15′，特别地使其适合于与用于通过直接气流流动来加热该分配器的电子终端相连。
分配器的另一可能形状如图2中所示。该容器为意大利专利申请No.MI2004A002279的目的且更详细地描述于其中。该分配器20由中心容器21和护罩22构成。容器21除开口23之外是封闭的；在该图中，其表示该容器具有三个开口的情形，其中一个被护罩遮盖住，但是可以存在任意数量的开口。护罩22同轴地布置在容器21周围，并且通过垫片24(仅显示了一个)保持在正确的位置上；该护罩在放射地对应于开口23的位置上具有开口25。在该容器中，存在本发明的锂盐与还原剂之间的混合物；在该情形中混合物表示为多个粒料26，其一个挨着另一个装载容器的底部。通过加热该容器来蒸发锂，例如通过接点27(仅显示了一个)将气流加入到容器端。
本发明将通过下列实施例进一步阐述。
实施例1
通过采用Inconel的板材(一种主要含镍-铬、和少量其它金属的合金)来制备类似于图1中所示的容器，厚度0.2mm。该容器的侧向尺寸为100×24mm，具有6mm高的凹槽，其中填充约10g重量比为5∶1的所述合金St 101和Li2TiO3的混合物；该混合物以直径为6mm和高度为3mm的粒料形式来使用，其通过将粉末混合物在约1700Kg的压力下压制而获得。
将该分配器置于抽空的室的底部上；将侧向尺寸为3×3cm的小玻璃板置于该分配器上约20cm的距离处。在容器端(图1中“翼”15、15′)施加100A直流电约6小时；气流流动加热分配器到约800℃的温度，由此引起混合物组分之间的反应和锂蒸发；一部分蒸发的锂在玻璃板上凝结，在其上形成薄膜。
试验期间，将该室连接于质谱仪的试样线，以监控蒸发期间排出的气体的量(显然把锂除外；由于凝结在室的冷壁上，该元素不能被送到MS测量中)；整个试验期间基本上未观察到气体溢出。
试验结束之后，通过测量试验之前和之后分配器的重量差，由此计算蒸发的锂的量；通过考虑在线MS测量的结果，该重量差完全归因于锂蒸发，由此实现了100％的金属蒸发。
分析形成于玻璃板上的膜并检查其纯度：将其溶解于HCl溶液中，并通过原子吸收法来分析这样获得的溶液；该膜含有的杂质量低于1wt％。
在该室内，靠近玻璃板的位置上，也安装了石英晶体监测器(QCM)，其为本领域众所周知的装置，通过利用石英晶体振动频率随其上沉积的材料的重量变化来测量薄膜的生长速率；由金属锂的已知密度和声阻抗，重量增加被认为与膜厚随时间的增加有关，由此获得恒定速率的膜沉积，数值为约0.2埃/秒
实施例2
制备类似于图2中所示的锂分配器，其包含圆柱形中心容器和护罩，二者均由厚度为0.2mm的不锈钢制成。该容器10cm长且直径为3.1cm，在其顶部部件上沿直线相距5cm具有2个直径2.5mm的孔隙；护罩同轴地安置在容器周围，其与容器一样长且直径为3.4cm，具有4个直径11mm的孔隙，两个孔隙朝向容器表面中的孔隙，另外两个位于前面两个孔隙之间并且彼此相距12mm。该容器填充有110g重量比为1∶1的所述合金St 101和Li2TiO3的混合物，该混合物以疏松粉末形式使用。
将该分配器置于抽空的室的底部上，并通过将直流电送到中心容器的两端来加热，由此引起锂蒸发；试验持续约40小时。该室中距离分配器36cm处存在QCM，以测量锂膜的生长速率，其与从分配器中蒸发相同金属的速率成比例。QCM通过反馈式线圈连接于电源，并且调节该体系以获得
的生长速率。随着蒸发的进行，分配器中剩余锂的量变得更少，并且保持该蒸发速率所需的温度增大；这就意味着，随着时间的推移需要更高能量，由此需要更高值的电流，最高电流值为300A(该体系可以提供的极限值)。
图3中报道了该试验的结果：曲线1表示膜沉积速率(FDR，以测量，在该图的左侧轴上)随沉积的锂膜厚度(T，以
测量)变化的趋势；曲线2表示试验期间在分配器末端测量的电压的趋势(伏特，V，该图的右侧轴)。
实施例3
重复实施例2的试验，区别仅在于，此时锂分配混合物以直径为6mm和高度为3mm的粒料形式存在，每个粒料重约0.3g，其是通过将粉末混合物在约1700Kg的压力下压制而获得的。
该试验的结果在图3中给出：曲线3表示蒸发速率的趋势，同时曲线4表示试验期间在分配器末端测量的电压的趋势。在整个试验期间曲线2基本上与曲线1重叠，除了在末尾观察到填充粉末或粒料的分配器行为的区别。
如实施例(尤其是实施例1)的试验中所观察到的那样，本发明的混合物适用于工业方法，因为它们显示稳定的金属蒸发特征，且不存在突发的现象，不会导致潜在有害气体(例如水)的实质溢出，并且能使得以可再现的方式和恒定速率生长高纯度的锂薄膜。实施2和3中所获结果的比较显示，虽然粉末和粒料二者都适用于本发明的目的，但是填充粒料的分配器可以是优选的，因为其能使锂以恒定蒸发速率蒸发更长时间(膜厚高达约
图3中曲线3；相对地，图3中曲线1，使用粉末获得的膜厚为约
)。这种行为的原因并未彻底弄清楚，但是认为，锂蒸发的操作温度下，疏松粉末相对于粒料具有更好的表面接触，并且由此变现为更好的电子导体；因此，当电流流过粉末时，相对于粒料产生了更少的热量，使用粉末的整体效果是，需要更高的电流来将混合物加热到有效引起锂蒸发的温度值。这种解释似乎得到了图3中两个曲线(3和4)的证实，在整个试验期间，填充粒料的分配器相对于填充疏松粉末的分配器，末端电压降更高。
Claims (10)
1.用于锂蒸发的混合物，其由锂盐和还原剂组成，其特征在于，锂盐选自Li2TiO3、LiTaO3、LiNbO3、Li2WO4和Li2ZrO3。
2.权利要求1的混合物，其中还原剂选自铝、硅、锆、钛、锆的合金或钛的合金。
3.权利要求2的混合物，其中所述合金选自重量百分比组成为Zr 84％-Al 16％的合金和重量百分比组成为Zr 76.5％-Fe 23.5％的合金。
4.权利要求1的混合物，其中所述锂盐和所述还原剂为粉末形式。
5.权利要求4的混合物，其中所述粉末的粒径小于1mm。
6.权利要求5的混合物，其中所述粉末的粒径小于500μm。
7.权利要求6的混合物，其中所述粉末的粒径为10-125μm。
8.权利要求1的混合物，其中锂盐和还原剂之间的重量比例为10∶1-1∶10。
9.权利要求8的混合物，其中所述重量比例为1∶5。
10.权利要求4的混合物，其中压制所述粉末混合物形成粒料。
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2004
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2005
- 2005-09-02 TW TW094130153A patent/TWI388501B/zh active
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- 2005-09-06 CN CN200580021281A patent/CN100575536C/zh active Active
- 2005-09-06 EP EP05778885.3A patent/EP1786946B1/en active Active
- 2005-09-06 US US11/570,816 patent/US7625505B2/en active Active
- 2005-09-06 KR KR1020077003072A patent/KR101195634B1/ko active IP Right Grant
- 2005-09-06 JP JP2007530857A patent/JP4804469B2/ja active Active
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2007
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| US3578834A (en) * | 1966-12-13 | 1971-05-18 | Getters Spa | Generation of alkali metals |
| CN1516249A (zh) * | 2003-01-09 | 2004-07-28 | 友达光电股份有限公司 | 一种薄膜晶体管的制作方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200621638A (en) | 2006-07-01 |
| WO2006027814A3 (en) | 2006-05-18 |
| US7794630B2 (en) | 2010-09-14 |
| TWI388501B (zh) | 2013-03-11 |
| HK1105538A1 (en) | 2008-02-15 |
| US20100021623A1 (en) | 2010-01-28 |
| EP1786946B1 (en) | 2014-02-26 |
| CN1981066A (zh) | 2007-06-13 |
| ITMI20041736A1 (it) | 2004-12-10 |
| KR20070050920A (ko) | 2007-05-16 |
| WO2006027814A2 (en) | 2006-03-16 |
| JP2008512570A (ja) | 2008-04-24 |
| KR101195634B1 (ko) | 2012-10-30 |
| US7625505B2 (en) | 2009-12-01 |
| US20080042102A1 (en) | 2008-02-21 |
| EP1786946A2 (en) | 2007-05-23 |
| JP4804469B2 (ja) | 2011-11-02 |
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