CN102119445A - 用于形成光伏器件的组合物和方法 - Google Patents
用于形成光伏器件的组合物和方法 Download PDFInfo
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- CN102119445A CN102119445A CN2009801316691A CN200980131669A CN102119445A CN 102119445 A CN102119445 A CN 102119445A CN 2009801316691 A CN2009801316691 A CN 2009801316691A CN 200980131669 A CN200980131669 A CN 200980131669A CN 102119445 A CN102119445 A CN 102119445A
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- reactive metal
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Images
Classifications
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- H—ELECTRICITY
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract
本发明提供了包括硅太阳能电池的光伏电池以及用于制造此类光伏电池的方法和组合物。在具有n型硅层的硅基底上提供有氮化硅层,反应性金属与所述氮化硅层接触,并且非反应性金属与所述反应性金属接触。烧制该组合件以在所述硅基底上形成由金属氮化物和任选地金属硅化物构成的低Shottky势垒高度触点以及与所述低Shottky势垒高度触点接触的导电性金属电极。所述反应性金属可以为钛、锆、铪、钒、铌、钽以及它们的组合,所述非反应性金属可以为银、锡、铋、铅、锑、砷、铟、锌、锗、镍、磷、金、镉、铍以及它们的组合。
Description
发明领域
本发明主要涉及硅太阳能电池器件。具体地讲,本发明涉及用于形成太阳能电池器件n型硅的电触点的组合物和方法。
发明背景
虽然本发明对诸如光电探测器和太阳能电池等光接收元件特别有效,但本发明还可应用于一系列半导体器件。下面以太阳能电池作为现有技术的具体实例对本发明的背景进行描述。
常规的地面太阳能电池一般由薄的硅(Si)晶片制成,其中已生成整流结或p-n结,并且随后已在晶片的两侧上形成导电的电极触点。具有p型硅基极的太阳能电池结构在基极或背面上具有正极触点,而在处于电池正面或光照面的n型硅或发射极上具有负极触点。“发射极”是为了产生整流结或p-n结而掺杂的硅层,并且与p型硅基极相比更薄。众所周知,在半导体的p-n结上入射的合适波长的辐射充当在该半导体中产生空穴-电子对的外部能量源。由于p-n结处存在电势差,空穴和电子以相反的方向跨过该结。电子移向负极触点,而空穴移向正极触点,从而引起能够向外电路输出功率的电流流动。太阳能电池的电极触点对于电池的性能较为重要。高电阻的硅/电极触点界面将阻碍电流从电池转移到外部电极,从而会降低效率。
制造的大多数工业晶体硅太阳能电池在正面都具有氮化硅减反射涂层(ARC)以最大限度地吸收阳光。如在许多出版物中所公开的,例如美国专利申请2006/0231801(Carroll等人),通常通过在减反射涂层上丝网印刷导体浆料并随后在高温下烧制来制造正面电极触点。常规的正面电极银浆包含银粉、有机粘合剂、溶剂、玻璃料,并可包含各种添加剂。银粉用作电极触点的主材料并提供低电阻。玻璃料可包含铅或其他低熔点成分以得到约300℃至600℃的软化点,从而在烧制期间玻璃料熔化并且用作“烧透”剂,其中氮化硅被穿透以使得银与n型硅接触。玻璃料还使烧结的银与硅相粘结。添加剂可用作另外的掺杂剂以改变n型传导性。在烧制期间,导电浆料烧结并透过氮化硅薄膜,从而能够与n型硅层发生电接触。这种方法一般被称为氮化硅的“烧透”或“蚀刻”。烧制后的界面结构由多个相组成:基底硅;银-硅岛状物;绝缘玻璃层内的银沉淀;以及大块烧结的银。因此,接触机理为通过银-硅岛状物和银沉淀以及穿过玻璃薄层的隧道效应的欧姆接触的混合。优化导电浆料的组合物和烧制温度分布图以使电池效率最大化。然而,金属-硅(MS)界面处玻璃的存在必然使其接触电阻比纯金属与硅接触所产生的电阻更高。
形成双极硅器件的低电阻触点存在困难。所有元素半导体触点都具有使触点整流的势垒。Shottky(肖特基)势垒高度(SBH)对穿过MS结的电导而言是整流势垒,因此该势垒高度对任何半导体器件的成功操作至关重要。SBH的大小反映了半导体多数载流频带边缘的势能与穿过MS界面的金属费米能级的错配。在金属/n型半导体界面处,SBH为导电带最小值与费米能级之间的差值。SBH越低,与硅的接触就越好。n型硅半导体器件的低Shottky势垒高度触点是已知的。例如,美国专利3,381,182、3,968,272和4,394,673公开了多种硅化物。当把金属放置成与硅接触并加热时,所述硅化物形成双极硅器件的低SBH触点。此类硅化物触点还未被用作硅太阳能电池的正面电极触点。
图1为以侧正视图示出的工艺流程图,其示出了使用常规方法和材料所进行的半导体器件的制造。
在图1A中,提供了p型硅基底10。该基底可由单晶硅或多晶硅组成。如图1B中所示,对于p型基底而言,形成图1B中的n型层20以制成p-n结。用于形成n型层的方法通常为使用三氯氧磷(POCl3)并利用供体掺杂剂(优选磷(P))的热扩散。扩散层的深度一般为约0.3微米至0.5微米(μm)。掺杂磷使硅的表面电阻减至介于几十欧姆每平方(Ω/□)至大约小于100欧姆每平方(Ω/□)之间。在不作任何特别改性的情况下,扩散层20在硅基底10的整个表面上形成。
接下来,用抗蚀剂或类似物保护该扩散层的一个表面,并且通过蚀刻从图1B的制品的除了一个表面之外的其他所有表面移除扩散层20。移除抗蚀剂,留下图1C的制品。
然后,如图1D所示,在上述n型扩散层上形成绝缘氮化硅Si3N4薄膜或氮化硅SiNx:H薄膜以形成减反射涂层(ARC)。Si3N4或SiNx:H减反射涂层30的厚度为约700至900埃。作为氮化硅的替代品,可将氧化硅用作减反射涂层。
如图1E中所示,在氮化硅薄膜30上丝网印刷正面电极的银浆50,然后进行干燥。此外,接下来在基底的背面上丝网印刷铝浆60和背面银浆或银/铝浆70,并相继干燥。然后在红外加热炉中,在大约700℃至975℃的温度范围内于空气中共烧正面和背面浆料几分钟至几十分钟。
如图1F所示,在烧制期间作为掺杂剂的铝从铝浆扩散到硅基底10中,从而形成包含高浓度铝掺杂剂的p+层40。该层一般被称为背表面场(BSF)层,它有助于改善太阳能电池的能量转化效率。
烧制还将铝浆60转化成铝背面电极61。与此同时,也在烧制背面银浆或银/铝浆70,继而变成银或银/铝背面电极71。烧制期间,背面铝与背面银或银/铝之间的边界呈合金状态,从而实现电连接。铝电极占据背面电极的大部分区域,这部分地是由于需要形成p+层40。由于向铝电极的焊接不可能,因此银背面片式电极在背面的某些部分上形成为电极,以用于借助铜带等元件互连太阳能电池。
在共烧期间,形成正面电极的银浆50烧结并渗入氮化硅薄膜30,因而能够与n型层20电接触。这种方法通常被称为氮化硅的“烧透”或“蚀刻”。这种烧透状态在图1F的层51中是明显的。
需要用于形成光伏器件的正面电极触点的新型组合物和方法,其可以使接触电阻显著降低并且保持粘附。需要用于形成硅太阳能电池的正面电极触点的新型组合物和方法,其可以免除玻璃界面的存在并且在保持粘附的同时提供优异的接触电阻。
发明概述
本发明公开了用于制造光伏器件的方法,其中提供了具有n型硅层的硅基底。在硅基底的n型硅层上形成氮化硅层。将反应性金属设置为与所述氮化硅层接触,并将非反应性金属设置为与反应性金属接触。烧制硅基底、氮化硅层、反应性金属和非反应性金属,以形成n型硅层的低Shottky势垒高度触点以及与低Shottky势垒高度触点接触的导电性金属电极。低Shottky势垒高度触点由一种或多种金属氮化物构成并且还可由一种或多种金属硅化物构成。反应性金属优选地为选自下列的一种或多种金属:钛、锆、铪、钒、铌、钽、以及它们的组合。非反应性金属优选地选自银、锡、铋、铅、锑、锌、铟、锗、镍、磷、金、镉、铍、以及它们的组合。
在一个优选的实施方案中,将反应性金属和非反应性金属相结合以形成金属组合物,并随后将该组合物沉积在氮化硅层上。在一个实施方案中,反应性金属为平均直径在100纳米至50微米范围内的颗粒形式,并且非反应性金属也可为平均直径在100纳米至50微米范围内的颗粒形式。优选地,反应性金属占所述组合物中总金属的1重量%至25重量%。
在一个实施方案中,在介于400℃和1000℃之间的温度下,烧制硅基底、氮化硅层、反应性金属和非反应性金属。在一个优选的实施方案中,烧制在还原性气氛下进行。
本发明还公开了用于制造硅太阳能电池的方法。根据此方法,提供具有n型硅层的硅基底并在该硅基底的n型硅层上形成氮化硅减反射层。将反应性金属放置成与氮化硅减反射层接触。烧制硅基底、氮化硅层和反应性金属,以形成n型硅层的低Shottky势垒高度触点。由一种或多种金属氮化物构成的低Shottky势垒高度触点还可包含一种或多种金属硅化物。
在一个优选的实施方案中,在烧制前将非反应性金属放置成与反应性金属接触,以形成与低Shottky势垒高度触点相接触的导电性金属电极。
反应性金属优选地为选自钛、锆、铪、钒、铌和钽的一种或多种金属,非反应性金属优选地为选自银、锡、铋、铅、锑、砷、锌、铟、锗、镍、磷、金、镉和铍的一种或多种金属。
可通过薄膜沉积将反应性金属和非反应性金属放置成与氮化硅减反射层接触。作为另外一种选择,可通过厚膜沉积将反应性金属和非反应性金属放置成与氮化硅减反射层接触。
还提供了用于生产光伏电池的厚膜组合物。该组合物包含一种或多种与氮化硅反应的金属,这些金属选自钛、锆、铪、钒、铌、钽、以及它们的组合。该组合物还可包含选自银、锡、铋、铅、锑、砷、锌、铟、锗、镍、磷、金、镉和铍的一种或多种非反应性金属。将反应和非反应性组分分散在有机介质中。反应性金属和非反应性金属为平均直径在100纳米至50微米范围内的颗粒形式。
附图简述
图1为以侧正视图示出的工艺流程图,说明了根据常规方法和材料所进行的半导体器件的制造。
图1中所示的附图标号说明如下。
10:p型硅基底
20:n-型扩散层
30:减反射涂层
40:p+层(背表面场,BSF)
50:正面上形成的银浆
51:银正面电极(通过烧制正面银浆获得)
60:背面上形成的铝浆
61:铝背面电极(通过烧制背面铝浆获得)
70:背面上形成的银浆或银/铝浆
71:银或银/铝背面电极(通过烧制背面银浆获得)
图2示出了自由能(ΔG)与温度的关系图,说明了氮化硅与氮化钛、氮化锆和氮化铪之间生成能量的巨大差异。
图3为通过诸如钛等反应性金属将氮化硅减反射涂层转化为导电性金属氮化物和金属硅化物的转化反应的示意图。
图4示出了多种金属、硅化物和氮化物对n型硅的Shottky势垒高度。
图5以侧正视图示出了根据本发明制造硅太阳能电池的方法。
根据惯例,下面讨论的附图的各个部件未必按比例绘制。附图中各个部件和元件的尺寸可能被放大或缩小,以便更清楚地说明本发明的实施方案。
发明详述
本发明公开了具有n型硅的低Shottky势垒高度电极触点的光伏器件。还公开了制备具有n型硅的低Shottky势垒高度电极触点的光伏器件的方法。所公开的光伏器件为太阳能电池,但也可以为具有n型硅的电极触点的其他光伏器件,例如光电探测器或发光二极管。所公开的实施方案为在n型硅上具有正面电极的太阳能电池,所述n型硅具有由氮化物以及任选的硅化物构成的低Shottky势垒高度电极触点。
如本文所用,术语“反应性金属”是指形成稳定的、高导电性的金属氮化物的金属或金属混合物,所述金属氮化物比氮化硅具有负值明显更大的生成自由能。此类金属包括过渡金属或它们的混合物,例如选自钛(Ti)、锆(Zr)、铪(Hf)、钽(Ta)、铌(Nb)和钒(V)的金属。由于负生成自由能的极大差异,这些反应性金属将通过氧化还原反应把氮化硅转化为高导电性金属氮化物。此类过渡金属氮化物通常具有式MzN,其中M为选自钛(Ti)、锆(Zr)、铪(Hf)、钽(Ta)、铌(Nb)和钒(V)的过渡金属,N为氮,z为1至2或在二者之间。可形成的过渡金属氮化物包括TiN、TaN、VN、V2N、ZrN、NbN、Nb2N、HfN以及它们的组合。图2中示出了该方法的热力学分析,该图显示了自由能(ΔG)与温度的关系图,以及氮化硅与氮化钛、氮化锆和氮化铪的负生成自由能的极大差异。
作为反应的一部分,如果反应性金属的含氮量大于氮化硅的含氮量,则反应性金属通过与氮化硅中的残余硅反应并接着与下面的n型硅反应,也将形成导电性金属硅化物。此类硅化物具有式MxSiy,其中M为过渡金属,例如选自钛(Ti)、锆(Zr)、铪(Hf)、钽(Ta)、铌(Nb)和钒(V)的金属,Si为硅,x可为1至5以及在二者之间,y可为1至3以及在二者之间。鉴于可能无法获得理想的化学计量,因此例如M1Si1中的x和y可略小于1或略大于1。可形成的金属硅化物包括Ti5Si3、TiSi、TiSi2、Ta2Si、Ta5Si3、TaSi2、V3Si、V5Si3、ViSi2、Zr4Si、Zr2Si、Zr5Si3、Zr4Si3、Zr6Si5、ZrSi、ZrSi2、HfSi、HfSi2、或它们的组合。
这些反应的热力学基本上为放热的,因此可通过烧制过程引发并迅速完成。以钛为例,氮化硅的转化和伴随的硅化钛的形成可近似地通过以下方程式表示:
Si3N4+7Ti→4TiN+3TiSi
图3示意性地示出了转化过程,其中通过钛将氮化硅转化为氮化钛和硅化钛。TiN和TiSi均具有高导电性。然而,其他导电性硅化物例如TiS2和Ti5Si3也可根据所存在的钛的量而形成。反应性金属非常难熔,并且由它们制成的氮化物和硅化物也是难熔的,因此转化反应的反应动力学可能非常缓慢,除非使用高温,例如大于800℃,并且就某段时间而言更优选地大于1000℃。然而,反应性金属以及它们的氮化物和硅化物的耐熔性使它们在硅中的扩散性和溶解度非常低,从而使它们成为用于维持硅太阳能电池中的高分流电阻的理想触点。
反应性金属可包含少量的某些稀土金属,例如镧(La)、铈(Ce)、镝(Dy)、铒(Er)、钬(Ho)、钆(Gd)以及类似的稀土金属,例如钪(Sc)和钇(Y),因为它们形成导电性很高的二硅化物和氮化物并且可以参与转化反应。
如图4所示,由上述反应形成的选自钛(Ti)、锆(Zr)、铪(Hf)、钽(Ta)、铌(Nb)和钒(V)的氮化物和硅化物具有大约0.5ev(电子伏特)的Shottky势垒高度(选自“Barrier Heights to n-Silicon”,Andrews等人,J.Vac.Sci.Tech 11,6,972,1974)。稀土(RE)硅化物的Shottky势垒高度也非常低,大约为0.3eV。因此,与银金属形成的用于太阳能电池中的n型硅的常规触点(约0.65ev)相比,反应性金属氮化物和硅化物形成n型硅的更低Shottky势垒高度触点。反应性金属氮化物和硅化物的其他优点在于它们非常容易被多种熔化的金属浸润。
如本文所用,术语“非反应性金属”是指不能将氮化硅转化为导电性氮化物和硅化物的金属或金属混合物。可选择非反应性金属以具有相对低的载流电阻率和与硅的相对弱的反应性。优选的非反应性金属还具有接近或甚至低于峰值烧制温度的熔点。可将金属组合物设计成具有多种元素以通过共晶成分的使用获得所需熔点。非反应性金属可选自但不限于以下金属,例如银(Ag)、锡(Sn)、铋(Bi)、铅(Pb)、砷(As)、锑(Sb)、锌(Zn)、锗(Ge)、镍(Ni)、金(Au)、镉(Cd)和铍(Be)。虽然磷(P)不是金属,但仍可包括在其中。可包含少量的其他金属,例如具有高熔点的其他金属(例如钯(Pd))以获得其他特定属性。金属混合物可包含砷或锑,因为它们可以另外作为供体掺杂剂在烧制期间选择性地掺杂浆料下面的硅以进一步降低它的表面电阻率并且改善接触电阻。非反应性金属组通常不包括硼(B)、铝(Al)、镓(Ga)、铟(In)和铊(Tl),因为它们可作为受体掺杂n型硅并且使表面电阻率升至过高。
可通过薄膜法或厚膜法将上述金属沉积在氮化硅上。薄膜法包括但不限于:溅射、金属蒸镀、化学气相沉积、原子层沉积、脉冲激光沉积等。将金属以它们的元素态沉积,并可沉积为单独的层或共同沉积以形成混合物或合金。通过此类薄膜法沉积的金属一般通过掩模或光致抗蚀剂沉积在氮化硅表面以限定所需的图案。
金属还可通过厚膜法沉积。厚膜法包括例如丝网印刷、喷墨印刷、或光成像技术。丝网印刷是有利的,因为它是一种高性价比的方法。在这种情况下,通过丝网将包含上述金属粉末的浆料印刷到氮化硅表面上。而丝网限定了所需的图案。
由反应性金属制成的丝网印刷浆料中使用的合适粉末应尽可能不含氧化物,以使得上述反应不会受到原有的反应性金属氧化物的干扰。由于反应性金属的氧化特性,它们会在空气中自动形成预定厚度的氧化物,所以粉末的粒度越大,总的氧化物含量越低。在还原性气氛中烧制粉末将会进一步阻止大量的氧化,但气氛的还原性必须非常强以便将反应性金属氧化物还原为金属。因此,最好使用与良好的厚膜浆料相容的最大粒度的粉末,以便所获得的特性使氧化物含量最低。为了获得最佳厚膜浆料特性,此类粉末的粒度应介于约100纳米至最大约50微米之间。
由非反应性金属制成的合适的粉末也应尽可能不含氧化物。此类粉末或贵金属,尤其是那些具有小的氧化物负生成自由能的粉末,它们的粒度可能比反应性金属小,因为在烧制过程中可以通过还原性气氛将氧化物还原为金属或它们不能形成氧化物。然而,那些具有负值更大的氧化物生成自由能的那些应该具有低氧含量并因此具有更大的粒度。
就厚膜沉积而言,通过机械混合将上述金属粉末与有机介质混合,以形成称为“厚膜浆料”的粘稠组合物,该组合物具有适于印刷的稠度和流变性。有机介质为临时性材料,因为它在烧制工艺的初始阶段被烧尽。可将多种惰性粘稠材料用作有机介质。有机介质必须使得金属粉末能够以适当的稳定度在其中分散。介质的流变性必须能赋予组合物良好的应用性能,包括:金属粉末的稳定分散、适于丝网印刷的粘度和触变性、合适的对衬底的浆料润湿性以及良好的干燥速率。用于所公开的厚膜组合物中的有机载体优选地为非水性惰性液体。可使用多种有机载体,所述载体可以包含或不包含增稠剂、稳定剂和/或其他常用添加剂。有机介质通常为聚合物溶于溶剂形成的溶液。此外,少量添加剂例如表面活性剂可以为有机介质的一部分。
最常使用的有机介质聚合物为乙基纤维素。其他有用的有机介质聚合物包括乙基羟乙基纤维素、木松香、乙基纤维素和酚醛树脂的混合物、低级醇的聚甲基丙烯酸酯和乙二醇单乙酸酯的单丁基醚。
存在于厚膜组合物中的最广泛使用的溶剂为醇酯和萜烯,例如α-或β-萜品醇或它们与其他溶剂例如煤油、邻苯二甲酸二丁酯、丁基卡必醇、丁基卡必醇醋酸酯、己二醇和高沸点醇以及醇酯的混合物。此外,在载体中可包含挥发性液体以便于载体在涂覆到基底上后快速硬化。对这些溶剂和其他溶剂的各种组合进行配制,以达到所需的粘度和挥发性要求。
根据所选的聚合物,有机介质中存在的聚合物占总组合物的1重量%至11重量%。可以通过有机介质将本发明的某些实施方案中可用的厚膜组合物调节至预定的可丝网印刷的粘度。
厚膜组合物中有机介质与金属组分的比率取决于涂覆浆料的方法和所用的有机介质类型并且可以变化。通常,为了获得良好的润湿,分散体包含70-95重量%的金属组分和5-30重量%的有机介质(载体)。
取决于烧制方法、沉积了多少反应性金属以及是否与残余硅或下面的n型硅发生反应,由氮化硅的转化所形成的低Shottky势垒高度触点可以与氮化硅具有大致相同的厚度(70纳米至100纳米)或可以为差不多几微米。然而,形成低电阻率电流载体以向外电路传送电流也是有利的。同样,低电阻的电极或附加的金属层是所期望的。这可以通过在烧制工艺之前或之后在反应性金属层上沉积非反应性金属层来实现。另一种方法是以合适的量将非反应性金属与反应性金属共同沉积。共沉积方式可以包括金属混合物或反应性金属与非反应性金属的合金。混合物或合金组合物中的反应性金属的量可根据氮化硅的厚度和沉积物的厚度进行定制,但通常反应性金属将占组合物中金属的约1%至25%。
如本文所述的具有低Shottky势垒高度的电极触点的太阳能电池可通过以下方法制造。
参见图5,提供图5A中所示的制品。该制品可包含单晶硅或多晶硅,并且包括p型硅基底10、n型扩散层20和减反射涂层30。图5A中所示的制品可按照以上关于图1D中所示的制品所述进行制备。
参见图5,提供图1D的制品并表示为图5A。参见图5B,铝浆60和背面银浆或银/铝浆70先后经丝网印刷并在基底背面上干燥。然后在大约700℃至975℃温度范围内的红外线加热炉中于空气中烧制背面浆料几分钟至几十分钟。烧制后形成图5C的制品。
参见图5C,如常规方法中一样,在烧制期间作为掺杂剂的铝从铝浆扩散到硅基底10中,以形成包含高浓度铝掺杂剂的p+层40。
烧制将铝浆60转化成铝背面电极61。与此同时,也在烧制背面银浆或银/铝浆70,继而变成银或银/铝背面电极71。烧制期间,背面铝与背面银或银/铝之间的边界呈合金状态,从而实现电连接。铝电极占据背面电极的大部分区域,这部分地是由于需要形成p+层40。由于向铝电极的焊接不可能,因此银背面片式电极在背面的某些部分上形成为电极,以用于借助铜带等元件互连太阳能电池。
现在,以对应于正面电极的指状和母线的图案(图5D中表示为80),通过厚膜或薄膜沉积法将本文所述的新型金属组合物涂覆在氮化硅绝缘薄膜30上。该沉积可通过将反应性金属和非反应性金属先后单独沉积在同样的图案上(两层均在图5D中表示为单层80),或者通过反应性金属和非反应性金属的混合物或反应性/非反应性金属合金的单次沉积来完成。作为另外一种选择,还可在没有非反应性金属情况下沉积反应性金属。
现在烧制沉积的金属组合物。通常在温度达400℃至1000℃的炉中进行烧制,而实际的温度取决于金属组合物。优选的是在此范围的低端温度下进行烧制,因为这将大大减少氧化问题。通常在还原性气氛中进行烧制,所述还原性气氛可包括真空、纯氮、氢气和氮气的混合物、或其他气体(例如氩气、一氧化碳和/或水)的混合物。此类气体混合物可用于在烧制过程中控制氧气的分压以避免金属氧化。防止氧化所需的准确的氧气分压(PO2)取决于金属组合物。完全防止金属氧化的气氛可通过热力学方法得自于作为温度计算函数的氧化物标准生成自由能,或如“F.D.Richardson and J.H.E Jeffes,J.Iron Steel Inst.,160,261(1948)”中所公开的图表。然而,一般来讲介于约10-6至10-18大气压之间的氧气分压(PO2)是合适的,因为非反应性金属将会显著稀释反应性金属。这一般可通过使用纯氮、一氧化碳/二氧化碳混合物、氩气、合成气体(氮气中含1%至4%的氢气)、氢气和氩气的混合物、或真空来实现。使用氩气是有利的,因为氩气可以防止反应性金属与氮气之间的任何反应。此类气氛不能完全防止反应性金属氧化,但是由于含有非反应性金属,氧化速率将会显著降低并且不会阻碍转化反应。就附加保护而言,可使用诸如钛板或调节器等氧气吸气器以清除气体中的氧气。
在烧制过程中优先形成熔化的反应性金属合金。由于通过液相的辅助加速了转化动力学,所以熔化的金属可允许降低转化反应温度。如果先沉积反应性金属接着沉积非反应性金属或两种金属作为混合物沉积,则非反应性金属会熔融并且迅速溶解反应性金属形成熔融合金。对于沉积的合金而言,金属熔化形成熔融合金。当金属熔化时,反应性金属优先通过熔化的金属迁移至氮化硅界面,并且与氮化硅反应形成反应性金属氮化物和硅化物。当反应性金属在界面处消耗时,更多的反应性金属迁移至界面参与反应。这种情况持续进行,直到熔融合金中的反应性金属在形成氮化物和硅化物过称中耗尽,或者通过停止烧制过程而终止该反应。在该过程中由于包含了熔化的金属,因此加速了氮化硅转化为反应性金属氮化物和硅化物的动力学,使得烧制可以在相对低的温度(例如介于400℃和1000℃之间)下完成。参见图5E,烧制形成了包括下列元件的电极:a)由减反射涂层30转化形成的并且反应性地粘结到下面的n型硅20的金属氮化物第一层90,b)在氮化物层90上形成的金属硅化物第二层91,以及c)由熔化的金属形成的金属第三层92。
尽管在烧制过程中优先地形成熔化的反应性金属合金,但烧制没有熔化非反应性金属并且转化过程在固态下进行是完全可行的。最后,对本文所述的工序进行修改,以使得本文所述的新型组合物可与背面浆料混烧也是可行的。
实施例1
按照对应于Ti与N比率为1的Ti0.2Sn0.8和Si3N4组合物的比例混合钛(Ti)金属粉末、锡(Sn)金属粉末和α氮化硅(Si3N4)。钛粉末小于325目或直径大约为35微米。锡的直径大约为0.1微米,α氮化硅的直径小于2微米。粒料由组合物通过压制所形成。然后在氩气中将粒料加热至800℃并在5、10和15分钟后取出粒料。预计800℃的烧制温度可形成并熔化组合物Ti0.2Sn0.8。用X射线照射粒料以检查反应产物。图6示出了烧制前和各个烧制时段后的X射线数据。可以看出并且正如所预期的那样,未烧制的粒料的X射线仅示出锡、钛和二氧化钛。所述二氧化钛为粉末表面上的氧化物层。由于α相是无定形的,因此氮化硅在X射线上没有显示。在经过不同时间的烧制之后,X射线数据显示已形成了氮化钛(TiN)和一些少量的硅化钛(Ti5Si3)。
实施例2
按照对应于Ti与N比率大于1的Ti6Sn5和Si3N4组合物的比例混合钛(Ti)金属粉末、锡(Sn)金属粉末和α氮化硅(Si3N4),以补偿钛上的表面氧化物并提供稍微过量的钛。钛粉末小于325目或直径为大约35微米。锡的直径为大约0.1微米,α氮化硅的直径小于2微米。粒料由组合物通过压制所形成。然后在氩气中将粒料加热至800℃并在5、10和15分钟后取出粒料。在这种情况下,预计800℃的烧制温度可形成Ti6Sn5但不会熔化组合物Ti6Sn5。用X射线照射粒料以检查反应产物。图7示出了X射线数据。可以看出且正如所料,未烧制的粒料的X射线数据表明只存在锡、钛和二氧化钛,并且钛含量明显高于实施例1中所示。其中二氧化钛为粉末表面上的氧化层。由于α相是无定形的,因此氮化硅在X射线上没有显示。在经过不同时间的烧制之后,X射线数据显示已形成了氮化钛(TiN)和硅化钛(Ti5Si3)。
实施例3
将在其表面上涂覆有大约70纳米氮化硅厚层的晶体硅太阳能电池基底放置在溅射室中,并在表面上共同沉积300纳米的钛和锡。计算沉积量,以使得氮化硅中对氮没有过量的钛。沉积物的组成将大致对应于Ti6Sn5。在形成气体(氮气中含4%的氢气)中于1000℃下将太阳能电池烧制30分钟。烧制后,用X射线检查太阳能电池的表面。图8示出了烧制前和烧制后的X射线。可以看出,正如所预期的那样在烧制前X射线主要是杂乱的。烧制后,可以明显地看出氮化钛(TiN)。
上述实施例表明,由于低熔点金属的存在,可在相对低的温度下通过钛反应性金属将氮化硅转化为导电性氮化物或硅化物或两者。所述实施例还表明,此转化可以如实施例1和2的粒料所证明的以粉末形式来完成,或如实施例3所证明的通过真空沉积的金属来完成。
Claims (23)
1.一种用于制造光伏器件的方法,所述方法包括:
提供具有n型硅层的硅基底,
在所述硅基底的n型硅层上形成氮化硅层;
将反应性金属放置成与所述氮化硅层接触,
将非反应性金属放置成与所述反应性金属接触,
烧制所述硅基底、氮化硅层、反应性金属和非反应性金属以形成所述n型硅层的低Shottky势垒高度触点以及与所述低Shottky势垒高度触点接触的导电性金属电极,所述低Shottky势垒高度触点由一种或多种金属氮化物构成。
2.如权利要求1的方法,其中,所述低Shottky势垒高度触点还包含一种或多种金属硅化物。
3.如权利要求1的方法,其中,所述反应性金属选自钛、锆、铪、钒、铌和钽。
4.如权利要求1的方法,其中,所述反应性金属还包括选自镧、铈、镝、铒、钬、钆、钪和钇的金属。
5.如权利要求1的方法,其中,所述非反应性金属为选自下组的一种或多种金属:银、锡、铋、铅、砷、锑、锌、锗、磷、镍、金、镉和铍。
6.如权利要求1的方法,其中,所述反应性金属与所述非反应性金属结合以形成金属组合物,并且随后将所述金属组合物沉积在所述n型硅层上。
7.如权利要求6的方法,其中,所述反应性金属为颗粒形式,所述颗粒具有在100纳米至50微米范围内的平均直径。
8.如权利要求7的方法,其中,所述非反应性金属为颗粒形式,所述颗粒具有在100纳米至50微米范围内的平均直径。
9.如权利要求6的方法,其中,所述反应性金属占所述金属组合物中总金属的1重量%至25重量%。
10.如权利要求1的方法,其中,在介于400℃和1000℃之间的温度下烧制所述硅基底、氮化硅层、反应性金属和非反应性金属。
11.如权利要求10的方法,其中,在还原性气氛中烧制所述硅基底、氮化硅层和反应性金属。
12.一种用于制造硅太阳能电池的方法,所述方法包括:
提供具有n型硅层的硅基底,
在所述硅基底的n型硅层上形成氮化硅减反射层;
将反应性金属放置成与所述氮化硅减反射层接触,
烧制所述硅基底、氮化硅层和反应性金属以形成与所述n型硅层接触的低Shottky势垒高度触点,所述低Shottky势垒高度触点由一种或多种金属氮化物构成。
13.如权利要求12的方法,其中,所述方法还包括以下步骤:在烧制前将非反应性金属放置成与所述反应性金属接触,以形成与所述低Shottky势垒高度触点接触的导电性金属电极。
14.如权利要求13的方法,其中,通过薄膜沉积将所述反应性金属放置成与所述氮化硅减反射层接触,并且通过薄膜沉积将所述非反应性金属放置成与所述反应性金属接触。
15.如权利要求13的方法,其中,通过厚膜沉积将所述反应性金属放置成与所述氮化硅减反射层接触,并且通过厚膜沉积将所述非反应性金属放置成与所述反应性金属接触。
16.如权利要求13的方法,其中,所述减反射涂层的厚度在70纳米至90纳米的范围内。
17.如权利要求13的方法,其中,所述低Shottky势垒高度触点还包含一种或多种金属硅化物。
18.如权利要求13的方法,其中,所述反应性金属为选自钛、锆、铪、钒、铌和钽的一种或多种金属,
并且所述非反应性金属为选自银、锡、铋、铅、锑、砷、锌、锗、镍、磷、金、镉和铍的一种或多种金属。
19.一种生产光伏电池的厚膜组合物,所述厚膜组合物包含:
一种或多种与氮化硅反应的金属,所述金属选自钛、锆、铪、钒、铌、钽以及它们的组合;
一种或多种选自银、锡、铋、铅、锑、砷、锌、锗、镍、磷、金、镉和铍的非反应性金属;
它们分散在有机介质中;
其中,所述反应性和非反应性金属为颗粒形式,所述颗粒具有在100纳米至50微米范围内的平均直径。
20.一种硅太阳能电池,所述硅太阳能电池具有由权利要求19的组合物形成的正面电极触点。
21.一种光伏器件,所述光伏器件包括:
包括n型硅层的硅基底;
设置并粘附在所述n型硅层上的低Shottky势垒高度触点,所述触点由金属硅化物构成,其中所述金属为钛、锆、铪、钒、铌、钽以及它们的组合;
粘附并设置在所述低Shottky势垒高度触点上的导电性金属电极。
22.如权利要求21的光伏器件,其中,所述低Shottky势垒高度触点还由金属硅化物构成。
23.如权利要求21的光伏器件,其中,所述导电性金属选自银、锡、铋、铅、锑、砷、锌、锗、镍、磷、金、镉、铍以及它们的组合。
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PCT/US2009/053375 WO2010019552A2 (en) | 2008-08-13 | 2009-08-11 | Compositions and processes for forming photovoltaic devices |
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JP (1) | JP2012500472A (zh) |
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CN113629155A (zh) * | 2021-08-06 | 2021-11-09 | 常州时创能源股份有限公司 | 一种晶硅太阳能电池 |
Also Published As
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EP2324511A2 (en) | 2011-05-25 |
CN102119445B (zh) | 2013-07-24 |
WO2010019552A2 (en) | 2010-02-18 |
KR20110050512A (ko) | 2011-05-13 |
US20130000709A1 (en) | 2013-01-03 |
US20100037942A1 (en) | 2010-02-18 |
WO2010019552A3 (en) | 2010-11-18 |
TW201019488A (en) | 2010-05-16 |
JP2012500472A (ja) | 2012-01-05 |
US8294024B2 (en) | 2012-10-23 |
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