CN102781660A - 基于脉冲激光烧蚀制造纳米颗粒溶液 - Google Patents

基于脉冲激光烧蚀制造纳米颗粒溶液 Download PDF

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CN102781660A
CN102781660A CN2011800089503A CN201180008950A CN102781660A CN 102781660 A CN102781660 A CN 102781660A CN 2011800089503 A CN2011800089503 A CN 2011800089503A CN 201180008950 A CN201180008950 A CN 201180008950A CN 102781660 A CN102781660 A CN 102781660A
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刘冰
车勇
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IMRA America Inc
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Abstract

本发明公开了一种基于脉冲激光烧蚀制备太阳光吸收化合物材料的纳米颗粒的方法。所述方法使用脉冲持续时间为10飞秒至500皮秒的脉冲激光束照射太阳光吸收化合物材料的靶材料，以烧蚀所述靶从而产生所述靶的纳米颗粒。收集所述纳米颗粒，并将所述纳米颗粒的溶液施加到基底上以制备薄膜太阳能电池。该方法维持了起始靶的化学计量性和晶体结构。该方法是一种成本显著更低的薄膜太阳能电池制造方法。

Description

基于脉冲激光烧蚀制造纳米颗粒溶液
相关申请
本申请要求2010年2月10日提交的美国临时申请序列号61/302995的权益。
关于联邦资助研究的声明
无。
发明领域
本发明涉及制备薄膜太阳能电池，且更具体涉及在液体中使用源材料的脉冲激光烧蚀来制备用于薄膜太阳能电池制造中的纳米颗粒溶液。
发明背景
与单晶太阳能电池相比，薄膜太阳能电池消耗显著更少的源材料且因此制造成本较低。在目前的薄膜太阳能电池制造中，作为最关键层的光吸收层通常是使用真空方法制造的，例如热蒸发、化学气相沉积和溅射。对于由以下构成的化合物太阳光吸收材料化合物，需要精确控制膜沉积：II-VI族元素如CdTe，或III-V族元素，或IB-III-VI2族元素如黄铜矿CuInSe2和CuIn1-xGaxSe2。控制组成元素之间的原子比例是确保正确的结构相和膜的所需电导率、空穴传导和良好的空穴迁移率的关键。例如，对于包含CuIn1-xGaxSe2的CIGS膜（其中x~0.2-0.3），组成元素之间的原子比例Cu:(In+Ga):Se应当接近25%:25%:50%，且允许的起伏小于几个百分比。从该组成比例的偏离会引起与电导率、固有缺陷行为、带隙和结构相有关的问题，从而最终降低太阳能电池的转换效率。
使用热蒸发来实现所需目的，这要求仔细监视和控制每种独立元素源的蒸发速率和蒸气束的均匀覆盖。此类制造工艺涉及在生产线内的复杂参数控制，这是该方法的高生产成本的主要因素。另外，存在与沉积均匀膜和前体相分离的困难相关的问题。
为了避免上述问题，开发了非真空和基于溶液的印制方法。在这些方法中，首先将元素源材料制成小的亚微米颗粒并分散到溶剂中。在与合适的粘合剂混合之后，溶液变为稠的糊料从而适合于印制薄膜。美国专利US6,268,014公开了一种基于机械研磨来制备亚微米尺度的金属氧化物和硒化物的细粉末的方法。然后以计算的重量比例将组成元素的前体粉末（即CuxO,In2O3,和CuxSe）混合并分散到溶液中从而制成用于喷印的糊料。与这种方法相关的一种困难涉及平均颗粒尺寸和尺寸分布，这些决定了堆积密度。机械研磨可产生亚微米颗粒直至几百纳米的颗粒，这仍在产物膜中留下数十纳米的未填充孔隙。因此为确保无针孔的层，人们需要使用更多材料从而提高了制造成本。
美国专利US7,306,823公开了一种制造被称为纳米油墨的纳米尺寸颗粒的溶液，其用于印制化合物CIGS膜。在该方法中，首先将元素源材料之一例如Cu制成纳米颗粒并将其分散到溶液中，所述纳米颗粒具有几十至几百纳米的直径。然后使用电化学方法用In层和Ga层涂覆这些Cu颗粒。这种工艺是耗时的并且非常昂贵。另外，对于恰当化学计量性的所需In层和Ga层的厚度取决于Cu芯的尺寸，这在具有大的尺寸分布时变得难以控制的。
对于简单的二元化合物材料例如CdSe的纳米颗粒，已存在许多成功的基于溶液的合成方法。然而对于复杂的材料例如CIGS，组成的精确控制仍具挑战性。例如，当使用金属氧化物作为前体时，需要高温氢还原来还原这些金属氧化物，这在时间和能量方面均非常昂贵。这是因为大多数金属氧化物在热力学上是非常稳定的，例如In2O3和Ga2O3的生成焓均低于-900kJ/mol，而水的生成焓是-286kJ/mol。不完全的还原将不仅导致杂质相而且还导致不适当的组成。
近年来，脉冲激光烧蚀已显示在各种液体中产生单质金属纳米颗粒。该方法是基于靶材料的激光引起的蒸发。典型的脉冲激光包括准分子激光和Nd:YAG激光，它们可提供脉冲持续时间为几纳秒（ns）且脉冲能量为几百毫焦耳（mJ）的激光脉冲。由于这些短激光脉冲极高的峰值功率（～GW），当它们聚焦在靶表面上时，定义为面积功率密度（以W/cm2计）或者当脉冲持续时间已知时更方便地定义为面积能量密度（以J/cm2计）的注量（fluence），易于超过大多数材料的烧蚀阈值，并且在照射下该材料被同时蒸发。当在液体例如水中进行烧蚀时，激光引起的蒸气在液体约束下快速地重新成核并且形成纳米尺寸的颗粒。已使用这种方法在水和其它液体中成功地制成贵金属纳米颗粒。
对于化合物材料，本方法的发明人近期证实，利用脉冲激光，意指脉冲持续时间为500皮秒以下的激光，可在烧蚀期间维持靶材料的组成使得产物纳米颗粒具有与靶相同的化学计量性组成。另外，这些产物纳米颗粒还维持与靶材料相同的晶体结构。据认为这些结果可能是在适当注量范围下进行脉冲激光烧蚀的直接后果。据推理当靶材料离解的时间尺度短于组成变化和结构改变的时间尺度时，在从块体靶向纳米颗粒产物的转变期间初始组成和晶体结构得以维持。
非常希望开发一种用于制造薄膜太阳能电池的方法，该方法快速、高度可重现并且比现有方法更廉价。还希望产生一种适合于各种起始材料并且不受起始材料限制的方法。
发明概述
本发明是一种基于脉冲激光烧蚀靶材料的单步方法，用以在液体中制造太阳光吸收化合物材料的纳米颗粒。这些纳米颗粒然后可用于制造薄膜太阳能电池。使用该方法，产物纳米颗粒维持起始材料的化合物组成和晶体结构。本发明是一种制备太阳光吸收化合物材料的纳米颗粒的方法，包括步骤：提供太阳光吸收化合物材料的靶；用脉冲激光束照射所述靶并烧蚀所述靶从而产生所述靶的纳米颗粒，所述脉冲激光束的脉冲持续时间为10飞秒至100纳秒，更优选为10飞秒至200皮秒；和收集所述纳米颗粒，其中所述纳米颗粒保持所述靶的化学计量性和晶体结构。
在多种实施方案中，靶材料由太阳光吸收化合物材料半导体制成。例如，显示了利用本发明制造CIGS纳米颗粒。作为一种四元化合物，CIGS是目前用于薄膜太阳能电池中的太阳光吸收器的最复杂的材料。本发明制备了具有适当化学组成的CIGS纳米颗粒。另外，本发明制备了具有恰当的CIGS黄铜矿晶体结构的CIGS薄膜。向溶液添加适宜的粘合剂材料可制备更稠的糊料从而使过程加速，且随后的退火能改善膜的品质。
附图简述
图1是依照本发明的激光烧蚀系统的示意图；
图2示意图解了依照本发明从纳米颗粒溶液形成薄膜的步骤；
图3显示了依照本发明制备的CIGS膜的横截面的电子显微照片；
图4显示了依照本发明制备的CIGS膜的能量色散X射线（EDX）谱；和
图5显示了依照本发明制备的CIGS膜的结构相的X射线衍射图。
发明详述
图1示意性图解说明了依照本发明用于在液体中制备复杂化合物的纳米颗粒的激光基系统。在一种实施方案中，从脉冲激光源（未显示）接收激光束1并且用透镜2进行聚焦。激光束1的源可以是种子激光器或本领域中已知的任何其它激光源，只要其具有如下所述的脉冲持续时间、重复率和功率水平。然后将聚焦的激光束1从透镜2通向导向机构3用以控制激光束1的移动。导向机构3可以是本领域已知的任何导向机构，包括例如压电镜（piezo-mirror）、声-光偏转器、旋转多边形、振动镜和棱镜。该导向机构3优选是能够实现激光束1的受控且快速移动的振动镜3。该导向装置3将激光束1引向靶4。该靶4由期望的太阳光吸收化合物材料制成，如下所述。例如，在一种实施方案中，其是具有期望的化学计量组成的CIGS盘片。其也可以是任何其它适宜的太阳光吸收化合物材料。靶4被浸没到液体5表面下方几毫米至优选小于1厘米的距离。不需要将靶4完全浸没到液体5中，只要靶4的一部分与液体5接触，激光束1可在靶-液体界面处进行烧蚀。容器7在其顶部具有可移去的玻璃窗6，该容器7为靶4提供了位置。O形环类型的密封件8位于玻璃窗6和容器7的顶部之间以便防止液体5从容器7中泄露出来。容器7包括入口12和出口14，因此液体5可越过靶4并且使得可被再循环。容器7任选地位于移动台9上，该移动台9可产生容器7的平移运动和液体5的移动。使用液体5的流动将产生的靶4的纳米颗粒10携带离开容器7以便在别处被收集。流体5的越过靶4的流动还可冷却激光距焦体积。液体5的流动速率和体积应当足以填充靶4和玻璃窗6之间的间隙。另外，其必须足以防止在激光烧蚀期间产生的任何气泡停留在玻璃窗6上。液体5可以是对激光束1的波长大体上透明的任何液体并且优选是靶材料4的不良溶剂。在一种实施方案中，液体5是电阻率大于0.05MOhm.cm且优选大于1MOhm.cm的去离子水。在其他实施方案中，其可以是挥发性液体例如乙醇或其它醇或者其可以是液氮或其混合物。当被收集的纳米颗粒10被收集并浓缩时或者将它们施加在基底上以形成薄膜太阳能电池时，使用挥发性液体作为液体5可具有益处。在烧蚀期间也可以将其他功能性化学试剂添加到液体5中。例如，可添加表面活性剂例如十二烷基硫酸钠（SDS）以便防止颗粒在液体5中聚结。典型的SDS摩尔浓度可为10-3-10-1摩尔/升(M)。当激光脉冲持续时间在200皮秒至100纳秒的范围内时，表面活性剂特别有助于制造无聚结的分散颗粒溶液。
在至少一种实施方案中，激光波长是1000纳米，其以最小的吸收率穿过水。激光脉冲重复率优选是100kHz以上。脉冲能量优选为1微焦耳（μJ）以上。本申请的受让人IMRA America Inc.公开了若干光纤基啁啾（fiber-based chirped）脉冲放大系统，这些系统提供从10飞秒至200皮秒的超短脉冲持续时间，1-100μJ范围的单脉冲能量，和大于10瓦特（W）的高平均功率。根据本发明使用的激光束的脉冲持续时间是10飞秒至100纳秒，更优选为10飞秒至200皮秒。脉冲能量优选为100纳焦耳至1毫焦耳且更优选为1μJ至10μJ。脉冲重复率为1Hz至100MHz，优选小于100MHz，且更优选为100kHz至1MHz。在多种实施方案中，根据本发明的烧蚀中使用的激光依次包括：具有30-100MHz的高重复率的种子激光器，该种子激光器还典型包括振荡器、脉冲展宽器、和前置放大器；光闸，其用以从所述种子激光器选择脉冲；和末级功率放大器，其将所选的脉冲放大。这些激光系统特别适用用于本发明。这些系统的波长典型为1030纳米。本发明不限于该激光束波长，相反地可使用二次谐波发生来产生可见光和紫外（UV）范围内的波长。通常，近红外（NIR）、可见光或UV区中的波长均可用于本发明。
在一种实施方案中，导向机构3是振动镜3，其配置用以激光束1在靶4表面上的快速光栅扫描（rastering）或其它移动。振动镜3的振动频率优选为10Hz以上，并且其优选具有0.1mrad以上的角振幅以及更优选1.0mrad以上的角振幅，使得靶4表面上的光栅扫描速度是0.01米/秒以上且更优选为0.1米/秒以上。此类镜3可以是压电驱动镜、电流计镜、或用于移动激光束1的其他适宜设备。
靶4可以是任何适宜的太阳光吸收化合物材料，包括二元、三元和四元化合物材料。适宜的二元化合物材料可选自元素周期表的IIB族和VIA族，例如CdTe和CdSe。适宜的三元化合物材料可选自元素周期表的IB族、IIIA族和VIA族例如CuInSe2和CuInS2。适宜的四元化合物材料可选自IB族、IIIA族和VIA族，例如CuInGaSe2和CuInGaS2。其它适宜的四元化合物材料可选自IB族、IIB族、IVA族和VIA族，例如Cu2ZnSnS4和Cu2ZnSnSe4。
在一种实施方案中，通过循环系统进行流体5穿过容器7的流动，且流动速度优选为1.0毫升/秒以上且更优选为10.0毫升/秒以上。流体5的流动对于使产生的纳米颗粒10在液体5中均匀分布以及将它们从容器7中移出是必要的。优选维持充足体积的液体5以避免在靶4上方液体5厚度的任何起伏。如果液体5厚度变动则其可能改变激光束1的光程性质并引起所产生的纳米颗粒10的尺寸的较宽分布。流动流体5上方的光学窗口6有助于在靶4上方保持恒定的液体5厚度。当循环系统不可用时，向移动台9引入横向振动移动，例如垂直于激光束1（如图1所示），也能够使液体5局部流过烧蚀点。移动台9优选具有几Hz的振动频率和几毫米的振幅。也可使用振动器来使液体5循环，其中振动器的循环移动使容器7内的液体5也具有循环移动，因此纳米颗粒10可均匀分布在液体5中。利用使液体5循环的这两种方法中的任一种，玻璃窗口6不是必须的；然而，使用任一种将在靶4上方的液体5厚度中引入非均匀性并且将引起较宽的纳米颗粒10的尺寸分布。
在一个实例中，靶是多晶CIGS的薄盘片。该靶中的组成元素Cu:In:Ga:Se之间的名义原子比率是25%:20%:5%:50%，根据靶制造商Konjudo Chemical Laboratory Co.Ltd.。该四元化合物材料CIGS具有1.0-1.2eV的带隙。使用波长为1000纳米的激光束，相应的光子能量是1.2eV，这高于该CIGS材料的带隙。激光束因此被这种靶材料强烈吸收。光吸收深度据估计小达～1μm。这导致低的烧蚀阈值，据估计该阈值为0.1J/cm2左右。在实施非本发明的方法中，典型的激光焦斑尺寸是20-40微米直径，更优选约30微米直径。使用30微米直径的焦斑尺寸，烧蚀CIGS所需的最小脉冲能量是约0.7μJ。
在本发明的实施中，将靶材料置于容器中并且当产生烧蚀的纳米颗粒时从液体中收集这些纳米颗粒。所述纳米颗粒优选具有2－200纳米的尺寸。如果需要，可通过本领域已知的过滤或离心分离将这些纳米颗粒浓缩。如果必要也可以进行这种操作来改变液体，以便随后将纳米颗粒施加到基底上。图2示出了从本发明方法产生的纳米颗粒制造薄膜太阳能电池的两个后续步骤。将纳米颗粒悬浮液20涂布到基底22上。在干燥之后，纳米颗粒悬浮液20的沉积物形成密堆的薄膜24。这两个步骤对于形成太阳能电池的大多数基于溶液的方法而言是常见的，并且本领域中已知添加适当的粘合剂以便制造较稠的糊料并且加速工艺。还已知的是在硒蒸气中对形成的膜24进行退火以便增强所述膜的结构品质。此类步骤可与本发明一起进行实施。可以使用各种基底22，包括半导体、玻璃、金属涂覆的玻璃、和金属板和金属箔。典型的金属基底包括但不限于钼、铜、钛和钢。
图3示出了根据本发明制成的CIGS膜的截面的电子显微图像。按如下方式对上述的CIGS盘片进行烧蚀。将靶盘片置于去离子水中，处在水表面下方3毫米处。将脉冲激光设定为500kHz的重复率、10μJ的脉冲能量、700飞秒的脉冲持续时间、和1000纳米的波长。用170毫米透镜将激光束聚焦到所述靶盘片上。在烧蚀期间该光束以2米/秒以上的线速度光栅扫描（rastered）。总烧蚀时间是约30分钟。然后将纳米颗粒溶液倒在硅基底上。在室温下于环境空气中使一滴溶液干燥从而获得薄膜。也可以同本发明一起使用其它施加方法例如刮涂（blade spreading）、旋涂、丝网印制和喷墨印制。
图4显示了上面关于图3所述的根据本发明方法制备的CIGS薄膜的能量色散x射线谱。鉴别所有四种组成元素Cu、In、Ga和Se的特征x射线发射。发射强度的定量分析给出该膜的Cu:In:Ga:Se原子比为21.3%:19.3%:4.7%:54.6%，这非常接近于上述初始靶的名义值。这证实本发明方法在纳米颗粒以及由它们制备的薄膜中维持了靶材料的组成。
图5显示了上面关于图3所述的根据本发明方法制备的CIGS薄膜的x射线衍射图。主要的衍射峰112、204和116证实该膜具有期望的CIGS黄铜矿晶体相。因此，本发明还制备出与靶材料具有相同晶体结构的纳米颗粒以及由它们形成的薄膜。发明人已发现，在室温下干燥CIGS膜之后，获得了期望的恰当黄铜矿微晶相。这证实了本发明的另一优点，即使用低处理温度的能力。尽管毫无疑问在硒气氛中进一步退火可进一步改善所制备膜的结构品质，然而在室温下成功制造出多晶CIGS膜将显著降低随后的退火步骤的能量成本。
虽然不希望受限于特定理论，本发明人进行如下推理：在根据本发明的脉冲激光烧蚀期间，特定激光引起的相转变导致化学计量性和晶体结构的期望维持。由于极短的激光脉冲，热和压力两者均快速积聚在照射体积内。瞬间温度可高达5000℃以及瞬间压力可达到GPa范围。这些极端条件的累积时间典型为2－30皮秒量级，允许可忽略不及的热和体积弛豫，特别是对具有低的载流子浓度的电介质。在这些极端条件下，材料去除以爆炸方式发生，其时间尺度为纳秒量级。这种时间尺度显著短于组成改变和晶体结构改变所需的时间，所述组成改变和晶体结构改变的发生典型需微秒以上。因此，在组成和晶体结构可发生改变之前烧蚀结束并且纳米颗粒产生。
已根据相关的法律标准描述了前述发明，因此本说明书是示例性的而非限制性的。所公开的实施方案的变体和变型对于本领域技术人员来说是明显的并在本发明的范围内。因此，通过研究以下权利要求书才能确定本发明提供的法律保护范围。

Claims (25)

1.一种由化合物靶生产太阳光吸收化合物材料的纳米颗粒的方法，包括步骤：
a）提供与液体接触的太阳光吸收化合物材料的块体靶；
b）用脉冲激光束照射所述靶并烧蚀所述靶从而产生所述靶的纳米颗粒；和
c）收集所述纳米颗粒，其中所述纳米颗粒保持所述靶的化学计量性和晶体结构。
2.权利要求1的方法，其中步骤a）包括提供二元化合物材料作为所述靶，该二元化合物材料由选自元素周期表的IIB族和VIA族的元素构成。
3.权利要求1的方法，其中步骤a）包括提供三元化合物材料作为所述靶，该三元化合物材料由选自元素周期表的IB族、IIIA族和VIA族的元素构成。
4.权利要求1的方法，其中步骤a）包括提供四元化合物材料作为所述靶，该四元化合物材料由选自元素周期表的IB族、IIB族、IIIA族、IVA族和VIA族的元素构成。
5.权利要求1的方法，其中步骤a）包括提供下列之一作为所述靶：CdTe、CdSe、CuInSe2、CuInS2、CuInGaSe2、CuInGaS2、Cu2ZnSnS4或Cu2ZnSnSe4。
6.权利要求1的方法，其中步骤a）包括提供铜、铟、镓、锌或锡的二元合金、三元合金或四元合金作为所述靶。
7.权利要求1的方法，其中步骤b）包括用脉冲持续时间在约10飞秒至10纳秒范围内的脉冲激光束照射所述靶。
8.权利要求7的方法，其中步骤b）包括用脉冲持续时间在约10飞秒至200皮秒范围内的脉冲激光束照射所述靶。
9.权利要求1的方法，其中步骤b）包括用脉冲能量在约100纳焦耳至10毫焦耳范围内的脉冲激光束照射所述靶。
10.权利要求1的方法，其中步骤b）包括用脉冲能量为约1微焦耳至10微焦耳的脉冲激光束照射所述靶。
11.权利要求1的方法，其中步骤b）包括用脉冲重复率小于约100MHz的脉冲激光束照射所述靶。
12.权利要求11的方法，其中步骤b）包括用脉冲重复率在约100kHz至1MHz范围内的脉冲激光束照射所述靶。
13.权利要求1的方法，其中步骤b）包括用波长在UV、可见光、近红外范围内的脉冲激光束照射所述靶。
14.权利要求1的方法，其中步骤b）包括使用振动镜在靶上移动所述激光束。
15.权利要求14的方法，其中所述振动镜具有10Hz以上的频率以及0.1mrad以上的角振幅，使得激光束焦斑在靶表面上以0.01米/秒以上的速度移动。
16.权利要求1的方法，其中步骤b）包括提供具有约20－40微米范围内的焦斑直径的脉冲激光束。
17.权利要求1的方法，其中步骤b）包括产生具有约2纳米至200纳米的尺寸分布的纳米颗粒。
18.权利要求1的方法，其中步骤a）包括提供浸没在液体中的靶以及其中所述步骤b）包括用脉冲激光束照射处在液体中的靶。
19.权利要求1的方法，其中步骤a）包括提供去离子水、有机溶剂或液氮作为所述液体。
20.权利要求1的方法，其中步骤a）所述液体还包含表面活性剂。
21.权利要求1的方法，其中步骤a）还包括使所述液体以1.0毫升/秒以上的速度循环流过所述靶。
22.权利要求1的方法，还包括如下步骤：
d）将收集的纳米颗粒施加到基底上从而在该基底上形成太阳光吸收薄膜。
23.权利要求22的方法，其中步骤d）还包括通过液滴涂布、旋涂、刮涂、丝网印制或喷墨印制将所收集的处在溶液中的纳米颗粒施加到基底上。
24.权利要求22的方法，其中步骤d）包括将所收集的纳米颗粒施加到基底上，所述基底包括半导体、玻璃、聚合物膜、金属、金属涂覆的玻璃、或金属箔，进一步包括使用钼、铜、钛之一或其混合物作为所述金属。
25.光伏太阳能电池器件，其包含通过权利要求22的方法制造的太阳光吸收层。
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