CN103459650A - 蒸镀装置和用于为其生产坩埚的方法 - Google Patents
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Abstract
本发明涉及蒸镀装置，其包含坩埚(1)和加热器(2)，该加热器被设置以用于加热在该坩埚(1)内的蒸发物料(3)，其中该坩埚(1)包含金属主体(11)和包含氧化钛(TixOy)的保护层(13)，其覆盖该金属主体(11)的内表面(12)至少一部分。此外，本发明涉及用于为这样的蒸镀装置产生坩埚的方法。
Description
技术领域
本发明涉及蒸镀装置，用于蒸镀薄膜，以及用于为这样的蒸镀装置生产坩埚的方法。
背景技术
这样的蒸镀装置，例如可用于蒸镀薄膜太阳能电池部分或全部薄膜到基板上。尤其是铜、铟、镓和硒的薄膜可被蒸镀到基板上，以生产所谓的CIGS(铜铟镓硒)太阳能电池。为此目的，该将被蒸镀的物料被置于该蒸镀装置的坩埚中并加热，而该基板则被置于该坩埚的开口的对面。加热在该坩埚内的物料使该物料被蒸发，并通过该开口离开该坩埚，以覆盖该基板。
由于该物料是在该坩埚内加热的，其可能与该坩埚本身的物料产生反应，而随着时间推移，可能会导致该坩埚表面腐蚀以及该坩埚在随后变质。有由钛制成的坩埚用于蒸发物料的例子。这样的坩埚已在例如US2008173241A和US2006096542A中公开。当在钛制坩埚内蒸发硒时，该坩埚腐蚀及随后效率降低的问题特别严重。这样的坩埚必须经常更换，导致生产成本高昂以及频繁停机。
在某些情况下，以氧化钛制成的坩埚已在蒸镀设备中使用。其中一个这样的例子是如在US2009061079A中所述般使用由氧化钛、氧化钽、氧化锆或氧化硅制成的坩埚，用于制造锂离子电池。整个坩埚使用这样的惰性物料会减轻与蒸镀物料产生反应的问题。然而，这样的陶瓷坩埚物料非常易碎，须十分谨慎处理。若处理不当，或当其被暴露于突然的温度变化中时，亦可能会容易碎裂，因而再次导致停机。
发明内容
本发明的目的是提出用于蒸镀一系列物料的可靠设备，其提供较低的保修成本，导致较强的扩散过程和有较长的运行时间。
本发明通过提供带有权利要求1的特征的蒸镀装置以及提供根据权利要求8所述的特征为这样的装置生产坩埚的方法，来实现该目的。本发明的有利实施例是该些从属权利要求的主题。
本发明以由金属制成的坩埚主体和把该金属物料从蒸镀物料分开的保护层所带来的综合优点为基础，从而保护该坩埚免受腐蚀。带有金属主体的坩埚有对温度变化敏感度较低的优点。此外，生产该坩埚的金属主体的成本可能比制造完全由陶瓷物料制成的坩埚低。
由于只有该坩埚的内部可能会与该蒸镀物料接触，故此以氧化钛(TixOy)保护层仅覆盖该坩埚主体的部分或全部内表面可能已经足够。然而，在其他实施例中，以保护层覆盖整个坩埚主体可能是有利的，其甚至可能更容易做到。
除了坩埚外，该蒸镀装置需要加热器，用于加热该蒸镀物料至蒸镀所需的温度，该蒸镀物料例如可以是硒，被放置在该坩埚内。虽然这样的加热可通过直接加热该蒸镀物料进行，但先加热该坩埚可能是有利的，使该蒸镀物料因而被间接加热。因此，该加热器可包含一个或多个靠近该坩埚或与其接触的电阻加热器。用于直接或间接加热该蒸镀/蒸发物料的其他加热器可包括感应加热器、激光加热器、离子加热器或其他合适的设备。
以该保护层覆盖该坩埚主体的步骤可在把新坩埚放在要用的蒸镀装置内之前进行。
该保护层可通过沉积方法于该坩埚主体的表面上产生，例如物理或化学沉积(如电镀氧化钛到金属表面上)。然而，在有利的实施例中，该保护层的氧化钛(TixOy)是诱导出来的氧化层。在这情况下，该氧化钛保护层通过氧化该坩埚主体内表面的所述部分产生。为了令此能实行，至少该坩埚的这个表面部分要由具有一定厚度的钛基合金制成。换言之，该坩埚主体可由分层的金属结构制成，其顶层或部分顶层包含钛基合金。
如果该保护层的氧化钛是诱导出来的氧化层，则可通过在氧环境或富氧环境下加热该坩埚主体产生，例如在熔炉内。
在有利的实施例中，该坩埚主体由钛基合金制成。其甚至可完全由钛基合金制成，而其后被氧化钛覆盖或其表面可被氧化，以形成氧化钛保护层。
钛基合金在本文文义中可以是任何主要组成元素为钛的金属合金。换言之，钛是 在钛基合金中比重最高的元素。该物料应含有足够的钛以形成氧化钛覆盖物。优选地， 这样的钛基合金的钛含量的重量百分比(wt%)至少为50。然而，钛的比例更高是有利的，如高于60wt%、高于70wt%、高于80wt%、高于90wt%、或高于95wt%。对本发明来说，钛基合金也可以是纯钛金属，或带有其他物料的污染物或杂质的钛金属。
在优选实施例中，该坩埚主体的钛基合金包含钯。替代地或额外地，可以添加其他元素到钛基合金，以改善其物理或化学特性。
在有利的实施例中，该坩埚主体由金属片制成。该金属片可通过轧制过程生产。该坩埚主体可由两片或更多片金属片接合制成。
覆盖至少该坩埚内表面一部分的保护层应优选地有至少50nm、至少100nm、至少150nm、至少200nm、至少300nm、或至少500nm的厚度。该保护层有一定的最低厚度是有利的，以保护该坩埚主体的金属。为此目的，几个或更少纳米的厚度可能会太薄。另一方面，如果该保护层太厚，则由于氧化钛结构易碎，其可能会剥落。这样该坩埚的表面将曝露出来，而且容易与该蒸发物料产生反应。
在该蒸镀装置的优选实施例中，提供了用于保持太阳能电池基板的装置，以用于将置于该坩埚内的蒸发物料蒸镀到该太阳能电池基板的表面上。这样的蒸镀装置例如可被设计成用于蒸镀一片或多片薄膜，用于制造薄膜太阳能电池，优选为铜铟镓硒太阳能电池。尤其，该蒸镀装置可被设计成以硒涂覆基板。因此，该保持装置将有利地 允许使大致长方形的玻璃面板置成与该坩埚的开口相邻。
该坩埚主体可在其被该保护层完全或部分覆盖之前，以任何合适的方法制造。可采用来为该坩埚主体制造金属物料的一个优选方法是轧制过程，即是金属的热轧制或冷轧制。以此方法生产的金属片然后就可被成型为该坩埚主体。替代地，可通过铸造熔化的金属或通过机械加工金属件而取得整个或部分坩埚主体。
附图说明
以下说明内容将参照所附的示意图，更详细解释本发明实施例的一些例子，其中：
图1展示出把物料从坩埚蒸镀到基板的设置；
图2和图3展示出根据本发明所述的蒸镀装置的坩埚的不同实施例；以及
图4a)至c)说明根据本发明一个实施例所述的用于生产坩埚的方法。
具体实施方式
图1展示出蒸镀设置的示意图，其包含由基板保持器5保持的基板4。基板4的表面41面向坩埚1，以蒸镀物料3将其填充。加热器2被布置于该坩埚1的周围，该加热器可加热该坩埚1并继而加热该蒸镀物料3，其因而蒸发和凝结到要以该蒸镀物料3涂覆的该基板表面41上。该蒸镀装置(包含该坩埚1和该基板保持器5)的其余部分在图1未被展示，例如在其中放置该坩埚1的真空室。
如果该坩埚1完全由金属制成，则当加热到足够程度时，该蒸镀物料(蒸发物料)3可能会与该坩埚1的内表面12产生反应。然而，根据本发明所述，该坩埚1的内表面12至少部分被保护层13覆盖。这样的坩埚1的有利实施例于图2和3中展示。
虽然图2所示的坩埚1具有圆柱形侧壁，并也可以是正方形、长方形、圆形或任何其他合适的形状，但图3所示的坩埚1为锥形。在这两种情况下，该坩埚1均包含坩埚主体11和保护层13，其覆盖该内表面12至少一部分。在图2及3所示的实施例中，该坩埚1整个内表面12被该保护层13覆盖。在其他优选的实施例中，该坩埚主体11可被该保护层13完全覆盖。
图2和3所示的坩埚各自设有加热器2，用于加热该蒸发物料(未于图2和图3展出)，以便将其蒸发到该基板4上。虽然在这里将其示意性地展出为电阻加热器，但该加热器2可包含任何类型的加热器，用于传递能量到在该坩埚1内的该蒸发物料3，从而让该蒸发物料3的粒子离开该坩埚1并被蒸镀到该基板表面41上。这样的设备的例子包括感应加热器、激光加热器、离子加热器和类似者。
图4a)、图4b)和4c)示意性地示出了根据优选实施例所述的用于制造带有保护层12的坩埚1的方法。为了此程序，如图4A)所示，设有由金属制成的坩埚主体11的坩埚1。该坩埚主体11例如可由从轧制过程取得的金属片制成。用于在此过程中使用的该坩埚主体11优选由钛基合金制成。
在后面的步骤中，如图4b)所示，该坩埚主体11被置于熔炉6内加热。在图4c)中示意性地展出了，通过在氧气环境中加热该坩埚，该坩埚的整个表面或(如与氧气的接触有限则)部分表面被氧化以形成该保护层。该保护层可透过沉积方法作额外强化，例如物理或化学沉积。可替代地利用这样的方法来产生该保护层。
权利要求书(按照条约第19条的修改)
1.蒸镀装置，其包含坩埚(1)和加热器(2)，该加热器被设置以用于加热在该坩埚(1)内的蒸发物料(3)，其中该坩埚(1)包含金属主体(11)和厚度为至少50nm且含氧化钛(TixOy)的保护层(13)，其覆盖该金属主体(11)至少一部分的内表面(12)，而该坩埚(1)的主体(11)是由钛或钛基合金制成。
2.根据权利要求1所述的蒸镀装置，其特征在于该保护层(13)的氧化钛(TixOy)是诱导出来的氧化层。
3.根据权利要求1或2所述的蒸镀装置，其特征在于该钛基合金包含钯。
4.根据前述权利要求中任一项所述的蒸镀装置，其特征在于该坩埚主体是由金属片制成的。
5.根据前述权利要求中任一项所述的蒸镀装置，其特征在于该保护层的厚度为至少50nm、至少100nm、至少150nm、至少200nm、至少300nm、或至少500nm。
6.根据前述权利要求中任一项所述的蒸镀装置，其特征在于用于保持太阳能电池基板的装置，放置在该坩埚(1)内的蒸发物料(3)会被蒸镀到该太阳能电池基板的表面上。
7.用于生产蒸镀装置的坩埚(1)的方法，其包括以下步骤：提供由金属物料制成的坩埚主体(11)和以厚度为至少50nm且含氧化钛(TixOy)的保护层(13)覆盖该金属主体(11)的内表面(12)的至少一部分，而该坩埚(1)的主体(11)是由钛或钛基合金制成。
8.根据权利要求7所述的方法，其特征在于该氧化钛保护层是由氧化该坩埚主体的内表面的所述部分产生。
9.根据权利要求7或8所述的方法，其特征在于该坩埚主体的金属物料于轧制过程中产生。
说明或声明(按照条约第19条的修改)
根据第19条第1段作出的声明
已在权利要求1中加入以下特征：
1.该保护层(13)有至少50nm的厚度。此特征原于权利要求6中公开，添加了该特征以进一步与所发现的现有技术区分。
2.该坩埚(1)的主体(11)由钛或钛基合金制成。此特征原于权利要求3及说明书第4页第3段中公开。添加了该特征以澄清，纯钛金属亦属于根据本发明所述的表述钛合金。
已对该方法权利要求(现为权利要求7)作出调整，使其与权利要求1一致。
Claims (10)
1.蒸镀装置，其包含坩埚(1)和加热器(2)，该加热器被设置以用于加热在该坩埚(1)内的蒸发物料(3)，其中该坩埚(1)包含金属主体(11)和含氧化钛(TixOy)的保护层(13)，其覆盖该金属主体(11)至少一部分的内表面(12)。
2.根据权利要求1所述的蒸镀装置，其特征在于该保护层(13)的氧化钛(TixOy)是诱导出来的氧化层。
3.根据权利要求1或2所述的蒸镀装置，其特征在于该坩埚主体是由钛基合金制成的。
4.根据权利要求3所述的蒸镀装置，其特征在于该钛基合金包含钯。
5.根据前述权利要求中任一项所述的蒸镀装置，其特征在于该坩埚主体是由金属片制成的。
6.根据前述权利要求中任一项所述的蒸镀装置，其特征在于该保护层的厚度为至少50nm、至少100nm、至少150nm、至少200nm、至少300nm、或至少500nm。
7.根据前述权利要求中任一项所述的蒸镀装置，其特征在于用于保持太阳能电池基板的装置，放置在该坩埚(1)内的蒸发物料(3)会被蒸镀到该太阳能电池基板的表面上。
8.用于生产用于蒸镀装置的坩埚的方法，其包括以下步骤：提供由金属物料制成的坩埚主体和以含氧化钛(TixOy)的保护层覆盖该金属主体的内表面的至少一部分。
9.根据权利要求8所述的方法，其特征在于该氧化钛保护层是由氧化该坩埚主体的内表面的所述部分产生。
10.根据权利要求8或9所述的方法，其特征在于该坩埚主体的金属物料于轧制过程中产生。
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| CN109972096A (zh) * | 2017-12-28 | 2019-07-05 | 核工业西南物理研究院 | 一种在料舟表面沉积金属涂层的方法 |
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| TWI470110B (zh) * | 2012-09-07 | 2015-01-21 | Manz Taiwan Ltd | 用於化學沉積設備的夾固裝置 |
| KR101582672B1 (ko) * | 2013-12-17 | 2016-01-05 | (주)알파플러스 | 증발용 도가니와 이를 포함하는 진공 증발원 및 진공 증착 장치 |
| WO2017217251A1 (ja) * | 2016-06-17 | 2017-12-21 | トーカロ株式会社 | 発熱部材 |
| SG10201608496UA (en) * | 2016-10-11 | 2018-05-30 | Au Optronics Corp | Crucible |
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| TW201233831A (en) | 2012-08-16 |
| WO2012103885A4 (de) | 2012-10-18 |
| US20140026815A1 (en) | 2014-01-30 |
| WO2012103885A1 (de) | 2012-08-09 |
| TWI576447B (zh) | 2017-04-01 |
| EP2670877A1 (de) | 2013-12-11 |
| DE102011000502A1 (de) | 2012-08-09 |
| JP6050255B2 (ja) | 2016-12-21 |
| KR20130110211A (ko) | 2013-10-08 |
| JP2014508860A (ja) | 2014-04-10 |
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