CN101346822A - 将金属初始层置换反应成cigss-太阳能电池的黄铜矿层的方法和装置 - Google Patents
将金属初始层置换反应成cigss-太阳能电池的黄铜矿层的方法和装置 Download PDFInfo
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Abstract
本发明涉及一种置换反应方法和一种置换反应装置，用于在RTP炉的反应室中以硫和/或硒将金属初始层(初始物质)置换反应成CIGSS－太阳能电池的黄铜矿层，特别是其目的在于制造薄层－太阳能模件。特建议，将敷层以初始物质的基片以及对反应足够用量的硫和/或硒置入一个可密封封闭的反应箱中，其被设有至少一个在反应室外部可控制的排出阀，该反应箱本身被置入抽真空的RTP－炉反应室中，反应室中具有基片的反应箱被加热到规定温度并在该温度下保持一确定的处理时间，其中在处理时间期间测量并通过至少一排出阀调节反应箱内的压力。
Description
技术领域
本发明涉及一种置换反应方法和一种实施其的装置，用于在RTP炉的反应室中以硫和/或硒将金属初始层(另也称作初始物质)置换反应成CIGSS-太阳能电池的黄铜矿层。特别是其目的在于制造薄层-太阳能模件。
背景技术
具有I-III-VI2-黄铜矿吸附层即称为Cu(InxGa1-x)(Sey，S1-y)2其中0≤x≤1且0≤y≤1形式之化合物的薄层-太阳能电池使得该电池的加工成本降低及效率高有了希望。
初始物质可以优选含有Cu和In/Ga或Cu、Zn、Sn。它们也可以含有其它元素如Ag、Sb、Sn、Zn或Fe。
初始物质层可以是在基片上的薄层(层厚0.1至5μm)，基片可以由玻璃、陶瓷、金属或塑料制成。
基片可以已经被预先敷以阻挡层，以便阻隔初始物质之来自玻璃的杂质。这些阻挡层可以是硅化合物例如氮化硅。
金属初始物质的置换是以(周期表)VI类的元素实现的，在本展示的方法中采用硫和/或硒(也称作硫族化物)。该置换(也称作反应)是在一个所谓的RTP-炉中通过能量输入于增高的温度下(快速加热过程)实现的。
公知的是一个硫族化物-供给源为初始物质(提供)以气态硫族化物，该气态硫族化物是在单独供源中由液态相被气化形成的并通过适合的输入装置例如硒喷淋装置被输入到反应室中，例如参见1994年Gabor等人的APP1.Phys.Lett 198-200页65(2)关于由(InxGa1-x)2Se3初始物质膜制成的高效CuInxGa1-xSe2太阳能电池。
还公开了一种通过挥发化合物(H2S或H2Se)工作的方法。挥发化合物通过适合的输入装置输入到反应室中。
此外，通常的是由气化源例如努森槽在高真空下气化硫或硒。
将固态的硫置入反应室中也是公知的(其中除了基片外，硫粉或硫片置入佩特里(Petri)-壳皿中)。
覆以初始物质的基片置入反应室中。反应室可以具有任意形状并可以由分别涂层或没有涂层的金属、玻璃或石墨制成。反应室可以含有开口和阀门(用于装料和卸料的开口-门、法兰、真空阀)并可以被抽真空(高真空区)。
具有初始物质的基片可以直接置入反应室内，其中它被安置在底部上或在适合的保持架内于垂直或水平方向上被调节或悬置。
DE 199 36 081 A1公开了一种在RTP-炉中热处理初始物质层的装置和方法，依此该覆层的基片置于一接受器中，其具有一个底部和一个玻璃陶瓷制的盖件。为了这样安置在接受器中，是从一侧给基片提供所要求的能量，而给初始物质是从另一侧，其中接受器的透明盖形成用于优选辐射区域的滤光器。但是这样制成的太阳能模件的效率比理论上或试验室规模中所可实现的数值要小的多。对于这些可实现的数值，请参见Siemer等的由快速热处理(RTP)得到的高效CuInS2太阳能电池、太阳能材料以及太阳能电池67(2001)，159-160以及Probst等的CIGSSE模式预先处理：摘自2003年5月12-16日，WCPEC-3，Osaka，提高性能的基础研究。
发明内容
本发明的目的在于提供一种上述类型的方法和装置，籍其可进一步提高所制成太阳能电池的效率。
本发明的目的通过权利要求1和5限定的特征方案解决。符合目的要求的结构方案是从属权利要求的技术主题。
依此，一个敷层以初始物质的基片以及对反应足够用量的硫和/或硒被置入一个可密封封闭的反应箱中，其设有至少一个在反应室外部可控制的排出阀，该反应箱本身被置入RTP-炉的反应室中。接着对反应室抽真空，同时该反应箱一起被抽真空，并且将反应室中具有基片的反应箱加热到一规定温度上并在该温度上保持一确定的处理时间。也可以想到，单独对反应箱进行抽真空。在处理时间期间测量并通过至少一个排出阀调节反应箱内的压力。
一个实施该方法适合的装置由一个敷层以初始物质的基片以及可装入对反应足够用量的硫和/或硒的可密封封闭的反应箱构成，该反应箱设有至少一个在反应室外部可控制的排出阀，反应箱的内部压力可通过一个传感器测量。
反应箱可以由金属、玻璃，陶瓷或石墨制成。它可以是覆层或没有覆层的、是透明的或非透明的。反应箱是密封的，即在进行处理时本身没有气体漏入反应室中，也没有气体从反应室进入反应箱中。反应箱具有在进行处理前和处理时调节压力的阀门。通过有目的之压力调节、特别是对硫压力的调节，以避免在进行处理时形成破坏性的杂质相。
当反应箱盖的弯曲变形可被测量时，该反应箱可直接应用于该处理过程-压力测量。
如上所述，在处理开始前即在加热前，反应箱被抽真空。对此，在反应开始前，可以在反应箱中调节一个确定的惰性气体背压。
硫族化物的输入(优选硫和/或硒)可以
·直接在反应室中进行，对此，一足够量的硫族化物提供给反应室；
·直接在反应箱中进行，对此，一足够量的硫族化物提供给反应箱；
·通过置入粉状物、小片状物、珠状物、片状物或其它固体形状物实现。
其中硫族化物可以分别置于反应室或反应箱的底部。
硫族化物也可以装入舟皿中，该舟皿可以敞口或部分被封闭。该舟皿由石墨、玻璃、陶瓷或金属制成；它们可以不覆层或覆层。
硫族化物的量与反应时的消耗量相匹配。只输入在反应时层所消耗的硫族化物量，因此，确保了消耗量的节省；否则多余的硫族化物会沉积在反应室或反应箱的壁上和/或被泵入反应室的真空泵中。
用于反应(将初始物质置换反应生成半导体黄铜矿层)的能量供给可以通过辐射器实现，辐射器设置在反应室内反应箱下面和/或上面。
能量供给还可以通过设置在反应室内的平面加热元件实现或可以通过设置在反应室内的电阻加热器实现。
能量供给以可调节的方式实现，以便根据反应的进行提供能量。
该方法的优点是：
-与公知方法的区别是，非常节省硫族化物。通过直接加入确定量的硫族化物以及通过与初始物质层反应的预期消耗量，可以尽可能地避免弄脏反应室和/或反应箱或真空泵。反应箱被密封封闭，以便提供用于反应的硫族化物且不会漏入周围的反应室或通过真空泵泵出。迄今通常在一定程度上敞开的系统中工作，因此不能保证节省使用的处理气体(硫族化物)。还有大量的剩余物会排到周围的环境中。
-通过采用反应箱和反应室，使得反应容积即必须加热和与硫族化物接触的容积保持很小。此外，反应压力可以通过采用反应箱由压力调节确定地调控，由此反应被按目的地控制。在由金属初始层反应成半导体黄铜矿层时，历经不同的化学相，它可以由反应箱中压力和温度被有目的地控制和调节。由此，可以避免不希望的反应副产物且可优选地调节所希望的反应。
-通过采用具有弹性盖的反应箱，可由盖的变形非常准确地确定反应箱中的压力。通过将压力信号与反应室中的气体流量调节器耦合，可使得反应室中压力与反应箱中的压力相适应。通过调节反应室和反应箱的阀门，可在反应时调节和有目的地改变反应箱中任何所希望的压力。
-与公知方法不同的是，采用无毒离析物工作，不需要使用有毒的硫或硒氢化物(H2S或H2Se)。此外，只采用绝对必需的硫族化物量，因为在封闭的系统中硫族化物不会泄漏且完全在反应时耗尽。
-反应室与反应箱的装料和卸料可以高度自动化，(由于)该反应箱可以在反应室外面被充以初始物质和硫族化物。
下面借助实施例进一步描述本发明。
附图说明
附图表明了该方法所采用的安置在RTP-炉之反应室中的反应箱的横截面图。
附图标记：
1反应箱
2盖
3过压阀
4调节阀
5基片
6反应室
7真空泵
8石英辐射器
9传感器
10压力传感器
11阀门
具体实施方式
反应箱1是一种低矮的石墨箱，它具有一由玻璃陶瓷制成的透明的盖2。反应箱1通过一个耐高温的密封被相对盖2密封。分别在反应箱1的端部设置包括一个包含过压阀3的集成阀以及一个调节阀4，通过调节阀4可以在作业期间以程序控制调节到所希望的压力。
为了反应箱1的装料和卸料，要将盖2移开。
反应箱1装有玻璃制成的基片5，在进行处理后由它(5)制成太阳能模件。基片例如被敷层以钼(层厚为0.1至2μm)、铜(层厚为0.1至2μm)以及铟(层厚为0.1至2μm)。除了该被覆层的基片5以外，还将元素形式的硫输入到反应箱1中。
反应箱1通过透明的盖2封闭，接着将反应箱1放入一个RTP-炉的反应室6中。
反应箱1借助真空泵7抽真空，接着关闭调节阀4并加热反应箱1。该加热在RTP-炉的反应室中通过石英辐射器8进行，石英辐射器8设置在反应室6中的反应箱1的上面和下面。在作业时，反应箱1被从室温加热到处理温度(300至600℃)。加热过程持续在1至60分钟之间。在加热过程期间，持续地测量反应箱1中的实际压力。其中弹性盖2的弯曲变形通过光学传感器9检测。另外，反应室6中的压力通过一压力传感器10测量。在加热过程中，通过整个的历程都调准并遵守特定的压力曲线。
在作业开始之前，在反应箱1中通过一阀门11输入的情性气体要调节到限定的压力(0.1至100hpa之间)。
在处理时间期间，初始物质层(以钼为基的铜和铟)历经确定的相。通过中间相CuIn2；Cu11In9和Cu16In9该初始物质与硫反应成CuInS2和Cu2S/Cu S。该温度曲线并主要是压力曲线被如此调节，以便由离析物只生成所希望的产物(CuInS2和Cu2S/CuS)，而不出现In(铟)和S(硫)之间的化合物。此外，还要避免富-铟(In)相在Cu-InS-系(例如CuIn6S8)中的形成。
通过加热反应箱，不仅具有初始物质层的基片5而且被输入的硫元素都被加热。这个(硫)经液态相变成气态相。硫的沸点可以通过预先调节的惰性气体-压力被准确地调节。反应箱中的最大压力建立则通过加入的硫量和反应箱1的调节温度被确定。在处理期间通过开启调节阀4可将处理压力调节到所希望的数值上。
在初始物质反应成CuInS2结束后，关断石英辐射器7并且反应箱1被冷却到室温。剩余的硫则在打开调节阀4后被泵入反应室6。所需要的硫量唯一地取决于初始物质的层厚并可以被精准地确定到小于30％剩余量、实际上甚至明显小于30％剩余量。由此，可确保对受保护之资源(这里为处理物质的加入量)的维护。
Claims (14)
1、一种置换反应方法，用于在一个RTP-炉的反应室中以硫和/或硒将金属初始层(初始物质)置换反应成CIGSS-太阳能电池的黄铜矿层，其特征在于：将敷层以初始物质的基片以及对反应足够用量的硫和/或硒置入到一个密封封闭的反应箱中，该反应箱至少设有一个在反应室外部可控制的排出阀，该反应箱本身被放入在RTP-炉的反应室中，该反应室被抽真空，将反应室中具有基片的反应箱加热到一个规定的温度并在这个温度上保持一个确定的处理时间，其中在该处理时间期间测量反应箱内的压力并通过至少一个排出阀调控它。
2、如权利要求1的方法，其特征在于：加热过程在惰性气体中进行。
3、如权利要求1或2的方法，其特征在于：硫或硒以固态形式置入反应箱中。
4、如权利要求1-3一的方法，其特征在于：硫或硒的量不大于反应所需量的30％。
5、一种置换反应装置，用于在一个RTP-炉中以硫和/或硒将金属初始层(初始物质)置换反应成CIGSS-太阳能电池的黄铜矿层，其特征在于：用于该RTP-炉之反应室中的加热过程设置一个反应箱，其可装入一个敷层以初始物质的基片以及其可输入一种对反应足够用量的硫和/或硒并且其是可密封封闭的以及其设有至少一个在反应室外部可控制的排出阀，其之内部压力通过一个传感器可以测量。
6、如权利要求5的装置，其特征在于：反应箱的盖是透明的。
7、如权利要求5或6的装置，其特征在于：反应箱的盖是弹性的。
8、如权利要求5-7之一的装置，其特征在于：反应箱的盖由玻璃陶瓷制成。
9、如权利要求5-8之一的装置，其特征在于：该盖被相对反应箱的壳体设有一个耐高温的密封。
10、如权利要求5-9之一的装置，其特征在于：反应箱另外设有至少一过压阀。
11、如权利要求5-10一的装置，其特征在于：用于测量反应箱内部压力的传感器是一个测量盖弯曲变形的光学传感器。
12、如权利要求5-11之一的装置，其特征在于：用于测量反应箱内部压力的传感器与一个用于流过反应箱气体的调节器连接。
13、如权利要求5-12之一的装置，其特征在于：在反应室内于反应箱上面和/或下面设置加热辐射器。
14、如上述权利要求5-13一的装置，其特征在于：反应室装有一个附加压力传感器。
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| PCT/EP2006/070178 WO2007077171A2 (de) | 2005-12-28 | 2006-12-22 | Verfahren und einrichtung zur umsetzung metallischer vorläuferschichten zu chalkopyritschichten von cigss-solarzellen |
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| EP1556902A4 (en) * | 2002-09-30 | 2009-07-29 | Miasole | MANUFACTURING DEVICE AND METHOD FOR PRODUCING THIN FILM SOLAR CELLS IN A LARGE SCALE |
| CN100456502C (zh) * | 2004-04-09 | 2009-01-28 | 本田技研工业株式会社 | 黄铜矿型薄膜太阳能电池用光吸收层的制造方法 |
| JP4416569B2 (ja) * | 2004-05-24 | 2010-02-17 | キヤノン株式会社 | 堆積膜形成方法および堆積膜形成装置 |
-
2005
- 2005-12-28 DE DE102005062977A patent/DE102005062977B3/de not_active Expired - Fee Related
-
2006
- 2006-12-22 CN CN2006800491844A patent/CN101346822B/zh not_active Expired - Fee Related
- 2006-12-22 US US12/159,082 patent/US20080305247A1/en not_active Abandoned
- 2006-12-22 EP EP06841601A patent/EP1966831A2/de not_active Withdrawn
- 2006-12-22 WO PCT/EP2006/070178 patent/WO2007077171A2/de active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007077171A2 (de) | 2007-07-12 |
| WO2007077171A3 (de) | 2007-08-23 |
| US20080305247A1 (en) | 2008-12-11 |
| CN101346822B (zh) | 2011-07-13 |
| DE102005062977B3 (de) | 2007-09-13 |
| EP1966831A2 (de) | 2008-09-10 |
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