CN101681945B - 高效率太阳能电池、其制造方法和制造设备 - Google Patents

高效率太阳能电池、其制造方法和制造设备 Download PDF

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CN101681945B
CN101681945B CN2008800178717A CN200880017871A CN101681945B CN 101681945 B CN101681945 B CN 101681945B CN 2008800178717 A CN2008800178717 A CN 2008800178717A CN 200880017871 A CN200880017871 A CN 200880017871A CN 101681945 B CN101681945 B CN 101681945B
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金宰湖
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Abstract

一种太阳能电池的制造方法，包括：在透明基底上依序形成第一电极与第一杂质掺杂半导体层；在所述第一杂质掺杂半导体层上形成第一本征半导体层；加热所述第一本征半导体层，以形成第二本征半导体层；及在所述第二本征半导体层上依序形成第二杂质掺杂半导体层与第二电极。

Description

高效率太阳能电池、其制造方法和制造设备
技术领域
本发明涉及太阳能电池，更特别涉及包括具有逐渐变化的结晶度的本征半导体层的高效率太阳能电池，以及所述太阳能电池的制造方法和设备。 
背景技术
针对因应石化资源耗尽、环境污染日增的清洁能源，如太阳能发电，近来研究的主题是使用阳光产生电动势的太阳能电池。 
太阳能电池从P-N(正-负)结层中被阳光激发的少数载流子的扩散产生电动势。单晶硅、多晶硅或非晶硅或化合物半导体可用于太阳能电池。 
因为使用单晶硅或多晶硅的太阳能电池有相对高的能量转换效率，使用单晶硅或多晶硅的太阳能电池有相对高的材料成本与相对复杂的制造过程。因此，在如玻璃或塑料的便宜基底上使用非晶硅或化合物半导体的薄膜太阳能电池已经有普遍的研究与发展。具体而言，薄膜太阳能电池在大型基底及挠性基底中有优势，使挠性大型太阳能电池能被制造。 
图1是根据现有技术的非晶硅薄膜型太阳能电池的截面图。在图1中，前电极12、半导体层13及后电极14依序形成在基底11上。透明基底11包括玻璃或塑料。前电极12包括用来透射来自透明基底11的入射光的透明导电氧化物(TCO)材料。半导体层13包括非晶硅(a-Si:H)。此外，半导体层13包括依序位于前电极12上的P型半导体层13a、本征半导体层13b及N型半导体层13c，形成PIN(正-本征-负)结层。本征半导体层13b可称作活性(active)层，其作为增加薄膜型太阳能电池的效率的光吸收层。后电极14包括TCO材料或金属材料，如铝(Al)、铜(Cu)及银(Ag)。 
当阳光照射在透明基底11上时，少数载流子扩散穿过透明基底11上的半导体层13的PIN结层，会在前电极12与后电极14之间产生电压差，从而产生电动势。 
与单晶硅太阳能电池或多晶硅太阳能电池比较起来，非晶硅薄膜型太 阳能电池具有相对低的能量转换效率。此外，当非晶硅薄膜型太阳能电池较长时间地曝露在光线中时，其效率会因性质恶化现象而进一步地降低，此称为Staebler-Wronski效应。 
为了解决上述问题，相关研究建议使用微晶硅(μc-Si:H或mc-Si:H)而不是非晶硅的薄膜型太阳能电池。在非晶硅与单晶硅之间作为中间材料的微晶硅具有约数十纳米(nm)到约数百纳米的粒度。此外，微晶硅没有非晶硅的性质劣化现象。 
微晶硅的本征半导体层因为较低的光吸收系数而具有约1μm到约3μm的厚度，而非晶硅本征半导体层具有约200nm到约500nm的厚度。此外，由于微晶硅的沉积率低于非晶硅层的沉积率，较厚的微晶硅比较薄的非晶硅有着更低的产量。 
再者，非晶硅的带隙为约1.7eV到约1.8eV，而微晶硅的带隙约为1.1eV，与单晶硅的带隙相同。因此，非晶硅与微晶硅具有不同的光吸收性质。因此，非晶硅吸收大部分波长在约350nm到约800nm的光，而微晶硅吸收大部分波长在约350nm到约1200nm的光。近来，以非晶硅与微晶硅之间有着不同光吸收性质为依据，依序形成非晶硅与微晶硅的PIN结层而具有串联(二重)结构或三重结构的太阳能电池已被普便使用。例如，当吸收大部分为较短波长带的光的非晶硅的第一PIN结层形成在阳光照射的透明基底上，且吸收大部分为较长波长带的光的微晶硅的第二PIN结层形成在非晶硅的第一PIN结层上时，会改善第一与第二PIN结层的光吸收，从而改善能量转换效率。 
发明内容
技术问题 
虽然与非晶硅或微晶硅的单一结构的太阳能电池比较起来，串联结构或三重结构的太阳能电池在能量转换效率方面有优势，但串联结构或三重结构的太阳能电池仍具有相对复杂的制造过程。再者，由于串联结构或三重结构的太阳能电池的制造过程包括微晶硅的沉积步骤，产量的改善会受到限制。 
技术方案 
因此，本发明涉及太阳能电池、太阳能电池的制造方法及太阳能电池的制造设备，能够消弥上述因现有技术的限制与缺点产生的一个或多个问题。 
本发明的一个目的为提供具有简化制造过程及改善产量的高效率太阳能电池，以及所述太阳能电池的制造方法与设备。 
本发明的另一目的为提供使用微晶硅与非晶硅作为光吸收层的高效率太阳能电池，以及所述太阳能电池的制造方法与设备。 
一种高效率太阳能电池的制造方法包括：在透明基底上依序形成第一电极与第一杂质掺杂半导体层；在所述第一杂质掺杂半导体层上形成第一本征半导体层；加热所述第一本征半导体层，以形成第二本征半导体层；及在所述第二本征半导体层上依序形成第二杂质掺杂半导体层与第二电极。 
在另一个方面，一种高效率太阳能电池包括：透明基底；第一电极，位于所述透明基底上；第一杂质掺杂半导体层，位于所述第一电极上；本征半导体层，位于所述第一杂质掺杂半导体层上，所述本征半导体层具有逐渐变化的结晶度；第二杂质掺杂半导体层，位于所述本征半导体层上；及第二电极，位于所述第二杂质掺杂半导体层上。 
在另一方面，一种太阳能电池的制造设备包括：传送腔室，包括用以传送基底的传送装置；加载互锁真空腔室，连接到所述传送腔室的第一侧部分，所述加载互锁真空腔室交错地呈真空状态与大气压力状态，用以输入、输出所述基底；第一处理腔室，连接到所述传送腔室的第二侧部分，所述第一处理腔室在所述基底上的第一电极上形成第一杂质掺杂半导体层；第二处理腔室，连接到所述传送腔室的第三侧部分，所述第二处理腔室在所述第一杂质掺杂半导体层上形成第一本征半导体层；第三处理腔室，连接到所述传送腔室的第四侧部分，所述第三处理腔室加热所述第一本征半导体层，以形成具有逐渐变化的结晶度的第二本征半导体层；及第四处理腔室，连接到所述传送腔室的第五侧部分，所述第四处理腔室在所述第二本征半导体层上形成第二杂质掺杂半导体层。 
在另一方面，一种太阳能电池的制造设备包括：装载腔室，交错地呈真空状态与大气压力状态，用以输入基底；第一处理腔室，连接到所述装载腔室的一侧部分，所述第一处理腔室在所述基底上的第一电极上形成第一杂质掺杂半导体层；第二处理腔室，连接到所述第一处理腔室的一侧部分，所述第二处理腔室在所述第一杂质掺杂半导体层上形成第一本征半导体层；第三处理腔室，连接到所述第二处理腔室的一侧部分，所述第三处理腔室加热所述第一本征半导体层，以形成具有逐渐变化的结晶度的第二本征半导体层；第四处理腔室，连接到所述第三处理腔室的一侧部分，所述第四处理腔室在所述第二本征半导体层上形成第二杂质掺杂半导体层；及卸载腔室，连接到所述第四处理腔室的一侧部分，所述卸载腔室交错地呈真空状态与大气压力状态，用以输出所述基底。 
在另一方面，一种太阳能电池的制造方法包括：在透明基底上依序形成第一电极与第一杂质掺杂半导体层；在所述第一杂质掺杂半导体层上形成光吸收层；加热所述光吸收层；及在所述光吸收层上依序形成第二杂质掺杂半导体层与第二电极。 
在另一方面，一种太阳能电池的制造方法包括：在透明基底上依序形成第一电极与第一杂质掺杂半导体层；在所述第一杂质掺杂半导体层上形成第一本征半导体层；结晶所述第一本征半导体层，以形成具有逐渐变化的结晶度的第二本征半导体层；及在所述第二本征半导体层上依序形成第二杂质掺杂半导体层与第二电极。 
有利效果 
在根据本发明实施方案的高效率太阳能电池中，由于作为光吸收层的线性晶体硅的本征半导体层包括非晶硅与微晶硅，光吸收带变广了，且能量转换效率改善了。此外，由于省略了分开的形成具有相对低沉积率的微晶硅层的步骤，与串联结构太阳能电池或三重结构太阳能电池的制造过程比较起来，根据本发明实施方案的高效率太阳能电池的制造过程是简化的。因此产量得以改善。 
附图说明
附图被包含在本说明书里，是说明书的一部分，使本发明更容易被了 解。附图阐明本发明的实施方案。 
图1是根据现有技术的非晶硅薄膜型太阳能电池的截面图。 
图2是根据本发明实施方案的太阳能电池制造过程的流程图。 
图3到图7是根据本发明实施方案的太阳能电池制造过程的截面图。 
图8是根据本发明另一实施方案的太阳能电池的RTP的截面图。 
图9是根据本发明实施方案的太阳能电池的集群型设备的平面图。 
图10是根据本发明实施方案的太阳能电池的在线型设备的平面图。 
优选实施方案 
以下将详细参考在附图中所示的实施方案。在许可的情况下，相似的组件符号会代表相似或相同的组件。 
图2是流程图，显示根据本发明实施方案的太阳能电池的制造过程，且图3至图7是根据本发明实施方案的太阳能电池的制造过程的截面图。 
在步骤ST11、ST12及图3中，提供有透明基底110，前电极120(即第一电极)与非晶硅的P型半导体层130(即第一杂质掺杂半导体层)依序形成在透明基底110上。前电极120包括用来透射来自透明基底100的入射光的透明导电氧化物(TCO)材料。例如，前电极120可具有约700nm到约2000nm的厚度。非晶硅的P型半导体层130具有约30nm的厚度。例如，非晶硅的P型半导体层130可通过使用SiH4、H2、B2H6、CH4的等离子增强化学气相沉积(PECVD)方法形成。 
在步骤ST13及图4中，非晶硅的第一本征半导体层140形成在非晶硅的P型半导体层130上。非晶硅的第一本征半导体层140作为光吸收层，并可具有约1μm到3μm的厚度。例如，非晶硅的第一本征半导体层140可通过使用SiH4、H2的PECVD方法形成。 
虽然在步骤ST13与图4中未表现出来，P型半导体层与第一本征半导体层140之间可形成缓冲层，以用来消除界面缺陷及调整带隙程度。例如，缓冲层可包括薄层的微晶硅或非晶硅。 
在步骤ST14及图5中，对非晶硅的第一本征半导体层140执行快速热制造过程(RTP)。例如在包括非晶硅的第一本征半导体层140的透明基底110传送进入加热腔室之后，非晶硅的第一本征半导体层140在氢(H2)的环境中，使用如通过以光学式加热的氙(Xe)灯或卤素灯的加热装置以一段长度的预定时间加热到约500℃至约600℃。加热的预定时间长度可以是在数分钟到数十分钟的范围内。非晶硅的第一本征半导体层不会完全通过RTP而结晶。而是，非晶硅的第一本征半导体层140被加热到使第一本征半导体层140的全部的非晶硅的约30％到约40％通过RTP而结晶。 
在步骤ST15与图6中，非晶硅的第一本征半导体层140通过RTP而结晶，以形成线性结晶硅的第二本征半导体层150。第二本征半导体层150具有沿着垂直于透明基底110的方向而逐渐变化的结晶度。因此，第二本征半导体层150中靠近加热装置的一部分具有比第二本征半导体层150中远离加热装置的一部分较高的结晶度。因此，第二本征半导体层150的结晶度与自第二本征半导体层150的底部表面的距离成正比。例如，第二本征半导体层150的结晶度可沿着从邻接透明基底110的底部表面到邻接加热装置的顶部表面的方向线性地增加。因此，线性结晶硅的第二本征半导体层150具有从接触P型半导体层130的底部表面线性增加到邻接加热装置的顶部表面的结晶度。例如，靠近接触P型半导体层130的底部表面的一部分可具有非晶硅，而靠近邻接加热装置的顶部表面的一部分可具有微晶硅。 
为了表示，第二本征半导体层150可分类为第一至第n个(nth)非常薄的层L1到Ln，所述薄层分别具有第一到第n个结晶度Xc(1)到Xc(n)。第一到第n个结晶度Xc(1)到Xc(n)满足以下方程式1。 
Xc(n)＞Xc(n-1)＞...Xc(2)＞Xc(1)-------------方程式1 
因此，当第一到第n个结晶度Xc(1)到Xc(n)分别具有第一到第n个带隙Bg(1)到Bg(n)时，第一到第n个带隙Bg(1)到Bg(n)满足以下方程式2。 
Bg(n)＜Bg(n-1)＜...＜Bg(2)＜Bg(1)-------------方程式2 
其中，第n个带隙Bg(n)是微晶硅的带隙，约为1.1eV，而第一个带隙Bg(1)是非晶硅的带隙，在约1.7eV与约1.8eV的范围之间。 
虽然根据本发明实施方案的太阳能电池不包括串联结构或三重结构的作为吸收层的非晶硅的PIN结层与微晶硅的PIN结层，因为第二本征半导体层具有如从非晶硅连续分布到微晶硅的结晶度，太阳能电池的光吸收带变广了，而涵盖较短波长带到较长波长带的范围。 
图8是示根据本发明另一实施方案的太阳能电池的RTP的截面图。 
在图8中，金属层190形成在非晶硅的第一本征半导体层140上，用来降低RTP的温度，以及增加结晶的速度。金属层190可包括镍(Ni)、铝(Al)及钯(Pd)中的至少一个。接着，使用如通过光学式加热的氙(Xe)灯或卤素灯的加热装置，执行金属层190与非晶硅的第一本征半导体层140的RTP。执行RTP时，金属层190的金属材料扩散进入第一本征半导体层140，形成金属硅化物。由于金属硅化物在通过RTP的结晶过程中作为晶核，第一本征半导体层140在约350℃至约450℃的相对低的温度下结晶，形成线性结晶硅的第二本征半导体层。此外，由于第一本征半导体层140因为金属硅化物的功能而以相对较短的预定时间通过RTP结晶，结晶速度增加了。特定地，金属层的RTP可以较有优势地应用在包括具有相对低耐热度的塑料透明基底的太阳能电池制造方法。在RTP之后，金属层可保留下来，并作为电极的一部分，或可被从第二本征半导体层移除。 
在步骤ST16与图7，非晶硅的N型半导体层(即第二杂质掺杂半导体层)与后电极170(即第二电极)依序形成在线性结晶硅的第二本征半导体层150上。非晶硅的N型半导体层160可具有约50nm的厚度。例如，非晶硅的N型半导体层160可通过使用SiH4、H2、PH3的PECVD方法形成。后电极170可包括TCO材料，或铝(Al)、铜(Cu)及银(Ag)中的一个。 
当相当于宽广波长带的阳光照射到太阳能电池的透明基底110上时，线性结晶硅的第二本征半导体层150吸收穿过P型半导体层130的阳光。由于第二本征半导体层150中与P型半导体层130的界面邻接的一部分具有较低结晶度，即具有较高比例的非晶硅，第二本征半导体层150中与P型半导体层130的界面邻接的所述部分吸收大部分相当于较短波长带的光线。此外，由于第二本征半导体层150中与N型半导体层160的界面邻接的一部分具有较高的结晶度，即具有较高比例的微晶硅，第二本征半导体层150中与N型半导体层160的界面邻接的所述部分吸收大部分相当于较长波长带的光线。因此，能改善根据本发明实施方案的太阳能电池的光吸收和能量转换效率。 
图9、图10是分别根据本发明实施方案的太阳能电池的集群型设备与在线型设备的平面图。 
在图9中，太阳能电池的集群型设备200包括传送腔室210、加载互锁真空腔室220及多个处理腔室，如第一到第四处理腔室230到260。加载互锁真空腔室220以及第一到第四处理腔室230到260环绕着并连接到传送腔室210。传送腔室210可包括如在腔室中的机器人的传送装置(未绘示)，以在各腔室之间传送基底。传送腔室210在太阳能电池的制造过程期间保持真空状态。加载互锁真空腔室220用来作为缓冲空间，用来在真空状态的传送腔室210与大气压力状态的外界之间传送基底。因此，加载互锁真空腔室220交错地呈真空状态与大气压力状态。 
例如，第一到第四处理腔室230到260连接到传送腔室210的侧部分。在第一处理腔室230中，P型半导体层130(图3)形成在透明基底110(图3)上，而在第二处理腔室240中，非晶硅的第一本征半导体层140(图4)形成在P型半导体层130上。此外，在第三处理腔室250中，第一本征半导体层140通过RTP结晶后变成线性结晶硅的第二本征半导体层150(图6)，而在第四处理腔室260中，N型半导体层160(图7)形成在第二本征半导体层150上。可以选择性地开启、关闭基底路径的开槽阀270设置在传送腔室210与加载互锁真空腔室220及第一到第四处理腔室230到260的各个之间。 
在上面具有前电极120的透明基底110被输入加载互锁真空腔室220之后，加载互锁真空腔室220抽空成具有真空状态的预定压力。接着，在加载互锁真空腔室220与传送腔室210之间的开槽阀270开启后，透明基底110通过传送机器人从加载互锁真空腔室220传送经过传送腔室210后进入第一处理腔室230。在第一处理腔室230中，P型半导体层130形成在前电极120上。在透明基底110传送到第二处理腔室240之后，第一本征半导体层140形成在P型半导体层130上，而在透明基底110传送到第三处理腔室250之后，第一本征半导体层140结晶而变成第二本征半导体层150。类似地，在透明基底110传送到第四处理腔室260之后，N型半导体层160形成在第二本征半导体层150上。接着，透明基底110从第四处理腔室260传送经过传送腔室210而到达加载互锁真空腔室220，而上面有前电极120、P型半导体层130、第二本征半导体层150、N型半导体层160的透明基底110从加载互锁真空腔室220输出。 
在图10中，太阳能电池的在线型设备300包括装载腔室310、第一到 第四处理腔室320到350以及卸载腔室360。装载腔室310、第一到第四处理腔室320到350及卸载腔室360以串联方式相互连接。基底被输入装载腔室310，并从卸载腔室360输出。装载腔室310、第一到第四处理腔室320到350及卸载腔室360的各个包括传送基底的在线型传送装置，如滚轮或线性马达。在太阳能电池制造过程期间，第一到第四处理腔室320到350保持真空状态。由于基底在大气压力状态的外界与第一到第四处理腔室320到350的各个之间传送，装载腔室310与卸载腔室360分别会交错地呈真空状态与大气压力状态。 
上面具有前电极120(图3)的透明基底110(图3)被传送到第一处理腔室320，且P型半导体层130(图3)形成在前电极120上。在透明基底110传送到第二处理腔室330之后，第一本征半导体层140(图4)形成在P型半导体层130上，而在透明基底110传送到第三处理腔室340之后，第一本征半导体层140结晶而变成第二本征半导体层150(图6)。类似地，在透明基底110传送到第四处理腔室350之后，N型半导体层160(图7)形成在第二本征半导体层150上。在上面具有前电极120、P型半导体层130、第二本征半导体层150、N型半导体层160的透明基底110从太阳能电池的在线型设备输出之后，后电极170(图7)可以在如溅射机的另一个设备中形成在N型半导体层160上。 
本技术领域人员会了解到，在不偏离本发明的范围或精神的情况下，本发明的太阳能电池与其制造设备及方法可以有各种修改与变化。因此，本发明希望涵盖在权利要求与等价物的范围内的修改与变化。 

Claims (6)

1.一种高效率太阳能电池，其包括：
透明基底；
位于所述透明基底上的第一电极；
位于所述第一电极上的第一杂质掺杂半导体层；
位于所述第一杂质掺杂半导体层上的第二本征半导体层，所述第二本征半导体层具有逐渐变化的结晶度，所述逐渐变化的结晶度通过加热位于所述第一杂质掺杂半导体层上的非晶硅的第一本征半导体层，使所述第一本征半导体层的全部的非晶硅的30％到40％通过快速热制造过程结晶而形成；
位于所述第二本征半导体层上的第二杂质掺杂半导体层；及
位于所述第二杂质掺杂半导体层上的第二电极。
2.如权利要求1所述的太阳能电池，其中所述第二本征半导体层包括线性结晶硅，以便所述第二本征半导体层的结晶度沿着从所述第二本征半导体层的底部表面到顶部表面的方向线性地变化。
3.如权利要求1所述的太阳能电池，其还包括位于所述第二本征半导体层与所述第二杂质掺杂半导体层之间的金属层。
4.一种制造太阳能电池的设备，其包括：
传送腔室，包括用以传送基底的传送装置；
加载互锁真空腔室，连接到所述传送腔室的第一侧部分，所述加载互锁真空腔室交错地呈真空状态与大气压力状态，以输入、输出所述基底；
第一处理腔室，连接到所述传送腔室的第二侧部分，所述第一处理腔室在所述基底上的第一电极上形成第一杂质掺杂半导体层；
第二处理腔室，连接到所述传送腔室的第三侧部分，所述第二处理腔室在所述第一杂质掺杂半导体层上形成非晶硅的第一本征半导体层；
第三处理腔室，连接到所述传送腔室的第四侧部分，所述第三处理腔室加热所述第一本征半导体层，使所述第一本征半导体层的全部的非晶硅的30％到40％通过快速热制造过程而结晶，以形成具有逐渐变化的结晶度的第二本征半导体层；及
第四处理腔室，连接到所述传送腔室的第五侧部分，所述第四处理腔室在所述第二本征半导体层上形成第二杂质掺杂半导体层。
5.一种制造太阳能电池的设备，其包括：
装载腔室，交错地呈真空状态与大气压力状态，用以输入基底；
第一处理腔室，连接到所述装载腔室的一侧部分，所述第一处理腔室在所述基底上的第一电极上形成第一杂质掺杂半导体层；
第二处理腔室，连接到所述第一处理腔室的一侧部分，所述第二处理腔室在所述第一杂质掺杂半导体层上形成非晶硅的第一本征半导体层；
第三处理腔室，连接到所述第二处理腔室的一侧部分，所述第三处理腔室加热所述第一本征半导体层，使所述第一本征半导体层的全部的非晶硅的30％到40％通过快速热制造过程而结晶，以形成具有逐渐变化的结晶度的第二本征半导体层；
第四处理腔室，连接到所述第三处理腔室的一侧部分，所述第四处理腔室在所述第二本征半导体层上形成第二杂质掺杂半导体层；及
卸载腔室，连接到所述第四处理腔室的一侧部分，所述卸载腔室交错地呈真空状态与大气压力状态，用来输出所述基底。
6.一种制造太阳能电池的方法，其包括：
在透明基底上依序形成第一电极与第一杂质掺杂半导体层；
在所述第一杂质掺杂半导体层上形成非晶硅的第一本征半导体层；
结晶所述第一本征半导体层，使所述第一本征半导体层的全部的非晶硅的30％到40％通过快速热制造过程而结晶，以形成具有逐渐变化的结晶度的第二本征半导体层；及
在所述第二本征半导体层上依序形成第二杂质掺杂半导体层与第二电极。
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