作者想感谢保罗Ciszek和Keith金刚砂从国家可再生能源实验室（NREL）的认证合资测量，莱利勃兰特（MIT）的光电子能谱测量，杰夫科特（ASU）为灵感的假设检验部分。这项工作是通过资助下的02.20.MC11博世能源研究网络支持的能源，通过合同DE-EE0005329的SunShot计划，美国能源部和罗伯特 - 博世LLC。五，斯氏，R.哈拉米略，和K.哈特曼承认的支持下，亚历山大·冯·洪堡基金会，美国能源部一个博士后EERE研究奖和英特尔博士研究生奖学金，分别。这使得工作中使用其屡获下ECS-0335765支持由美国国家科学基金会纳米系统中心在哈佛大学。

1.基材的选择和切削<ol><li>购买抛光硅片厚厚的热氧化。对于此报告的设备，使用500微米厚的硅片用300纳米或更厚的热氧化。该基板的选择标准将在讨论部分讨论。 </li><li>旋涂晶片的具有典型的正性光刻胶的抛光面（SPR 700或PMMA答495）和软烘烤（30秒，在100℃）。 注意:这是一个保护层，以防止在随后的切割步骤损坏或污染。 </li><li>使用一个模具锯到晶片切成1"×1"（25.4×25.4毫米2）正方形的基板。 </li></ol> 2.基板清洗<ol><li>除去颗粒和其他残留物而导致的使用压缩氮气枪切割步骤，随后进行超声浴在去离子（DI）水进行5分钟，在45 - 60℃。 </li><li>用超声波巴除去光致抗蚀层个在丙酮中5分钟，在45 - 60℃。 </li><li>清洗暴露的衬底3随后超声浴中，所有为5分钟，在45 - 60℃:丙酮，乙醇，和异丙醇。光洁度通过用压缩氮气枪干燥，同时基片留在石英载体。 </li></ol> 3.莫溅射<ol><li>加载干净的Si / SiO 2的衬底输送到一个高真空溅射系统。确保基材板是未加热的并且衬底旋转被启用。用于在商用系统用倾斜磁控管枪2"的目标和大约4投掷距离"这里报告的设备，工艺。 </li><li>在相对较高的背景压力的Ar例如10毫托沉积所述第一层（粘合层）。用于此处报道的设备，过程与180W的溅射功率（DC），这给了2.6埃/秒的生长速度，以及第一钼层，其为360纳米厚。 </li><li>沉积第二层（导电层）在相对较低的背景压力的Ar例如2毫托。使用相同的溅射功率为第一层（180瓦）和沉积相同的厚度。 注:这里所报告的设备有一个第二钼层为360nm厚，同第一层。 </li><li>莫沉积后，存放在真空下的基板，直到SnS的沉积步骤。 </li></ol> 4. SnS的沉积注意:ALD沉积技术在子部分4.1中描述，并且TE沉积在子部分4.2中描述。在ALD沉积系统示于图2和TE沉积系统示于图3。 <ol><li>存款的SnS通过ALD <ol><li>前装载到反应器中，放入钼基板在UV臭氧清洁器5分钟，以除去有机粒子。然后将基片的基片支架上，然后插入到沉积区。 </li><li>稳定炉坦佩叉涂抹在200℃开始沉积之前。 </li><li>从双（N，N- -diisopropylacetamidinato&#39;） -锡（II）锡（MEC（N -iPr）2）2，这里称为锡（AMD）2]和硫化氢（H反应生长的SnS薄膜2 S）4。 <ol><li>保持锡（AMD）2前体在95℃的恒定温度。用纯N 2气以从容器协助的锡（AMD）2蒸气递送在烤箱到沉积区。在每个ALD循环，供给三个剂量锡（AMD）的2前驱体为1.1托秒的总暴露。 </li><li>在N 2中使用的4％的H 2 S的气体混合物作为硫源。确保暴露于硫化氢汽是每剂量1.5托秒。确保的 H 2 S的分压和H 2 S的氮气的总压是0.76毫米汞柱和19乇，分别。 </li></ol></li><li>集合T他锡前体的剂量和H 2 S的剂量之间泵送时间仅为1秒（短相比大多数其它常规的ALD过程），以加速的沉积。 注意:因为Sn的前体没有完全被这短抽时间除去一些残余锡前体，当硫化氢到达保持。因而，处理可以被描述为一个脉冲CVD工艺。的SnS薄膜的生长速率为0.33埃/循环，或0.04埃/秒。 </li></ol></li><li>存款的SnS由TE <ol><li>确保处理腔室的压力为2×10 -7乇或更低。负载衬底输送到通过负载锁定腔室中。持基板的板或者与单个片段，或者与与被拧紧到衬底板适当大小的口袋定制基板支架。 </li><li>斜源和基片加热器为额定值。对于这里报告设备中的基板温度为240℃，生长速率为17; /秒;为实现这一增长率设置源温度范围为550 - 610℃（所需的源温度随时间源粉末的单个负载）。目标膜厚度为1000nm。 </li><li>前后的SnS薄膜沉积通过移动QCM臂进入处理室后使用石英晶体监视器（QCM）测量沉积速率。对于该测定将衬底升高，使得QCM可以移动到衬底生长的位置。 注:沉积速率仍然相当稳定整个3小时的沉积时间（±0.05 /秒偏差）。 </li><li>沉积之后，放空到空气之前转移样品放回负载锁。通过空气中迅速运送样品到存储无论是在真空中或在下一处理步骤之前在惰性气氛手套箱中。 注意:典型无意空气暴露时间大约为3分钟。典型的储存时间是一天和AW之间伊克。 </li></ol></li></ol> 5. SnS的退火注意:此步骤是为ALD和TE的太阳能电池进行略有不同。对于ALD太阳能电池的退火步骤中的子节5.1中描述，并且对于TE太阳能电池的过程中的子节5.2中描述。退火的目的是在讨论部分讨论。 <ol><li>退火的ALD生长的SnS薄膜的硫化氢气体。 注意:在用于ALD生长同样的系统中进行该步骤。 <ol><li>在40 SCCM和10毫米汞柱压力流量用纯硫化氢气体（纯度99.5％）。 </li><li>加热的SnS薄膜的400℃的温度并保持1小时在H 2 S的气体的环境中。确保该气体流动在整个过程中，包括温度斜坡上升和下降。 </li></ol></li><li>退火TE生长的SnS薄膜的硫化氢气体。执行此步骤中的一个专用的管式炉。 <ol><li>第负荷Ë样品到一个干净的石英板和滑动到炉的热区的区域。 </li><li>熔炉被密封后，吹扫三次，纯的N 2，并允许抽空到基础压力。 </li><li>建立气流在100sccm的4％的H 2 S在28乇。 </li><li>坡道的温度至400℃，用10分钟。持在400℃下1小时，然后让样品冷却无助于热区。保持常数为H 2 S的气流和压力直到样品冷却到低于60℃。取出样品并且立即进入下一个步骤，或将它们放入存储在惰性气体的手套箱。 </li></ol></li></ol> 6. SnS的表面钝化了天然氧化物注意:此步骤是为ALD和TE的太阳能电池进行略有不同。在子部分6.1 ALD太阳能电池的表面钝化步骤进行说明，而对于TE太阳能电池的过程中的子部分中描述6.2。本步骤的功能是在讨论部分进一步讨论。 <ol><li>对于ALD生长的样品，通过ALD生长一层薄薄的SnO 2。 注意:我们使用不同的反应器比用于SnS的增长。 <ol><li>成长的SnO 2由锡的环状酰胺的反应[（1,3-双（1,1-二甲基乙基）-4,5-二甲基- （4R，5R）-1,3,2- diazastannolidin -2-亚基）锡（Ⅱ）]和过氧化氢 ​​（H 2 O 2）。存储环状酰胺锡前体在烘箱中于43℃，并且在一个鼓泡器在RT为H 2 O 2。 </li><li>保持在120℃下沉积基底的温度。 </li><li>露出的锡前体和H 2 O 2的用在每个周期0.33和1.5乇第二，分别为共5个循环。检查所得的SnO 2的厚度为0.6 0.7纳米，如通过X射线光电子能谱（XPS）分析10测定。 </li></ol></li><li>对于TE生长样本，形成THISnO 2的空运曝光N层。 <ol><li>暴露样品到实验室环境空气24小时。检查所得的SnO 2的厚度为约0.5纳米，通过XPS分析测得的。 注意:典型RT是24±1℃，和典型的湿度为45％±13％（在夏天更高）;对于这里报告的装置，所述值分别为24.6℃和&lt;30％，分别为。 </li></ol></li></ol> 7.沉积锌（O，S）/ ZnO缓冲层注意:在一个用于SnS的生长通过ALD同一ALD处理室中执行该步骤。 <ol><li>长出的Zn（O，S）:N层通过ALD。 <ol><li>保持在120℃的基板温度。 </li><li>生长的Zn（O，S）:N通过ALD从二乙基锌的（锌（C 2 H 5）2，DEZ），去离子水（H 2 O），4％的H 2 S在N 2和氨的反应（NH 3）11。存储起泡，包含3宁DEZ在RT。使用一个周期序列[DEZ-H 2 O-DEZ-NH 3] 14 - [DEZ-H 2 S] 1，重复这个超级循环12次。确保氨曝光11秒托。 </li><li>检查，在所得膜的S / Zn的比率为0.14，如通过卢瑟福背散射光谱学12测定，该膜的厚度为约36纳米。 </li></ol></li><li>生长ZnO层通过ALD。 <ol><li>保持在120℃的基板温度。 </li><li>生长的ZnO与DEZ-H 2 O的50 ALD循环 注意:得到的ZnO膜的厚度为约18纳米。 </li></ol></li></ol> 8.沉积的透明导电氧化物的（TCO），氧化​​铟锡（ITO）的<ol><li>切从0.024 ITO荫罩"使用实验室激光切割机（610微米）铝板材6061。 注:面具定义是0.25厘米2 11的矩形设备大小加在一个角较大垫是用于光反射的测量，参见图4。 </li><li>安装设备和口罩的掩模对准。 注意:这是在铝板具有嵌套口袋用于衬底和掩模和夹子来固定掩模在适当位置。 </li><li> ITO存款反应磁控溅射。 <ol><li>加热衬底至约80 - 90℃，使基板旋转。 </li><li>使用一个直径为2英寸的ITO靶（的In 2 O 3 / SnO 2的90/10重量％，99.99％纯）在65瓦RF溅射功率为40 / 0.1标准立方厘米的Ar / O 2气体流量在4毫乇的总压力。 </li><li>长出了240纳米厚的ITO膜。 注意:对于这些参数，为0.5埃/秒和薄层电阻的范围增长率40 - 60Ω/□得以实现。 </li></ol></li></ol> 9.金属化<ol><li>从127微米厚的奥斯汀切割金属荫罩ITIC不锈钢板材。 注意:这些面具是由一家商业公司切断与+ 10 / -5微米的公差。金属图案由2个手指1.5mm的分离，每组7毫米长，和一个1×1毫米2接触垫， 见图4。 </li><li>安装的装置和口罩的掩模对准，如在步骤8.2。 </li><li>存款银（为TE设备）或Ni / Al为（对于ALD设备）通过电子束蒸发。 <ol><li>安装掩模对准到一个电子束金属蒸发系统的衬底板。抽空至低于1×10 -6乇的基础压力。 </li><li>蒸发金属以2埃/秒的速率。存500纳米金属总厚度。 </li></ol></li></ol> 10.器件特性<ol><li>在黑暗中和在AM1.5模拟太阳光线的所有设备- （"V J"）的测量进行电流-电压。 <ol><li> V数据FR -通过收集Ĵ校准太阳模拟器嗡一个校准的硅太阳能电池和调节所述太阳模拟器的灯功率和高直到达到为AM1.5太阳辐射的校准的电流值。 </li><li>通过使用铍铜双探头尖端接触到两个顶（阳极，银或铝）和底部（阴极，钼）层接触四线模式的设备。联系底层由刮掉缓冲和SNS层用手术刀刀片。 </li><li>测量光与暗的J -使用源米的由采购电压和电流测量V数据。 注:设备通常的范围内测量±0.5 V.该装置不响应于所述电压扫描的方向或速率。在常规试验的区域限定光孔不使用时，看到更多细节讨论部分。 </li></ol></li><li>在所有设备上执行的外部量子效率（EQE）的测量，带可变灯光和偏压。 <ol><li>通过测量respo校准EQE系统NSE一个硅光电二极管校准的。 注:该软件这些数据与NIST支持的标准进行相应的调整光量进行测量比较。 </li><li>使用四线方法中，如在步骤10.1.2接触的设备。 </li><li>使用商业系统，该系统照射单色光样品切碎，在100赫兹以上270 1100纳米的波长范围内，并测量所产生的电流测量的EQE。根据制造商的标准操作程序进行该测量。 </li><li>重复EQE测量可变电压和白光偏见。使用源表，以提供电压偏置，和卤灯提供的光偏置。测量正向设备和反向电压偏置，并根据可变白色光强度可达〜1太阳。 </li><li>测量使用分光光度计用积分球以在ITO上表面的光学反射率（％R）转换成外部到内部量子效率（IQE）。根据制造商的标准操作程序进行该测量。 </li></ol></li></ol>

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基材的选择清洗 氧化Si晶片用作衬底。所述底物是用于将所得的太阳能电池的机械支撑，和它们的电学性能并不重要。硅片是首选，因为玻璃市场购买硅晶片通常比商业购买玻璃晶片清洗剂，这可以节省时间，基板清洗。 Si衬底还具有比玻璃，从而导致生长和退火过程中加热更均匀的导热性。与商购的玻璃晶片，发现有必要清洗用洗涤剂的基材，包括一个手动擦...

薄膜光伏（PV）继续吸引兴趣和显著研究活动。然而，光伏市场的经济正在迅速转变，发展商业成功的薄膜光伏已经成为一个更具挑战性的前景。在片为基础的技术制造的成本优势不再是理所当然 ​​的，并提高效率和成本必须寻求平等1,2鉴于这种现实，我们选择开发的SnS作为吸收材料的薄膜光伏。 SnS的有可能转化为低制造成本的内在实用性强等优点。如果高的效率可以证明，它可以被认为是一个简易替换为CdTe的商用薄膜PV。这里，对于最近报道记录的SnS太阳能电池的制造过程是证明。我们专注于实际问题，如基材的选择，沉积条件，设备布局和测量协议。 的SnS由无毒，地球丰富和价廉的元件（锡和硫）。的SnS是惰性和不溶性半固体（矿物名Herzenbergite）为1.1电子伏特的间接带隙，强的光吸收与能量光子以上1.4电子伏特（α&gt; 10 4 -1），和固有P型导电率与载流子浓度在范围10月15日至 10月一十七日cm -3的3 - 7重要的是，SnS的蒸发的同成分，是相稳定到600℃的8,9-这意味着SnS的可通过热蒸发（TE）和它的高沉积。 - 速度表弟，封闭空间升华（CSS），如采用碲化镉太阳能电池的制造。这也意味着，SnS的相位控制远比大多数薄膜PV材料更简单，特别是包括铜（在，Ga）的（S，硒）2（CIGS）和Cu 2 ZnSnS 4（CZTS）。因此，细胞EFFICIENCY代表的主要障碍SnS的光伏商业化，和SNS可以被认为是一个简易替换的碲化镉一次高效率的证明在实验室规模。然而，这种效率的障碍不能被夸大。我们估计，在记录效率，必须由四个因素增加，从〜4％至〜15％，以刺激商业开发。显影的SnS作为高品质的SnS薄膜的简易替换为碲化镉也将需要生长的CSS，和其上的SnS可以直接生长的n型伙伴材料的发展。 下面描述的步骤的分步过程，使用两种不同的沉积技术，原子层沉积（ALD）和TE制造记录的SnS太阳能电池。 ALD是一个缓慢增长的方法，但至今已取得最高效率的设备。 TE是更快和工业上可伸缩，但滞后的ALD在效率。除了不同的SnS沉积方法中，TE和ALD太阳能电池退火，表面钝化，和金属化的步骤稍有不同。器件制造步骤被列举在图1中。 描述手术后，检测结果为认证记录设备和相关样品展示。在创纪录的业绩已有报道。这里的重点是对结果的典型处理运行的分布。

<table><tbody><tr><td>Quartz wafer carrier</td><td>AM Quartz, Gainesville, TX</td><td></td><td>bespoke design</td></tr><tr><td>Sputtering system</td><td>PVD Products</td><td></td><td>High vacuum sputtering system with load lock</td></tr><tr><td>4% H&lt;sub&gt;2&lt;/sub&gt;S in N&lt;sub&gt;2&lt;/sub&gt;</td><td>Airgas Inc.</td><td>X02NI96C33A5626</td><td></td></tr><tr><td>99.5% H&lt;sub&gt;2&lt;/sub&gt;S</td><td>Matheson Trigas</td><td>G1540250</td><td></td></tr><tr><td>SnS powder</td><td>Sigma Aldrich</td><td>741000-5G</td><td></td></tr><tr><td>Effusion cell</td><td>Veeco</td><td>35-LT</td><td>Low temperature, single filament effusion cell</td></tr><tr><td>diethylzinc (Zn(C&lt;sub&gt;2&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;)</td><td>Strem Chemicals</td><td>93-3030</td><td></td></tr><tr><td>Laser cutter</td><td>Electrox</td><td>Scorpian G2</td><td>Used for ITO shadow masks</td></tr><tr><td>ITO sputtering target (In&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;/SnO&lt;sub&gt;2&lt;/sub&gt; 90/10 wt.%, 99.99% pure)</td><td>Kurt J. Lesker</td><td>EJTITOX402A4</td><td></td></tr><tr><td>Metallization shadow masks</td><td>MicroConnex</td><td></td><td>bespoke design</td></tr><tr><td>Electron Beam Evaporator</td><td>Denton</td><td></td><td>High vacuum metals evaporator with load-lock</td></tr><tr><td>AM1.5 solar simulator</td><td>Newport Oriel</td><td>91194</td><td>1,300 W Xe-lamp using an AM1.5G filter</td></tr><tr><td>Spectrophotometer</td><td>Perkin Elmer</td><td>Lambda 950 UV-Vis-NIR</td><td>150 mm Spectralon-coated integrating sphere</td></tr><tr><td>Calibrated Si solar cell</td><td>PV Measurements</td><td></td><td>BK-7 window glass</td></tr><tr><td>Double probe tips</td><td>Accuprobe</td><td>K1C8C1F</td><td></td></tr><tr><td>Souce-meter</td><td>Keithley</td><td>2400</td><td></td></tr><tr><td>Quantum efficiency measurement system</td><td>PV Measurements</td><td>QEX7</td><td></td></tr><tr><td>Calibrated Si photodiode</td><td>PV Measurements</td><td></td><td></td></tr><tr><td>High-throughput solar cell test station</td><td>PV Measurements</td><td></td><td>bespoke design</td></tr><tr><td>Inert pump oil</td><td>DuPont</td><td>Krytox</td><td>PFPE oil, grade 1514; vendor: Eastern Scientific</td></tr><tr><td>H&lt;sub&gt;2&lt;/sub&gt;S resistant elastomer o-rings</td><td>DuPont</td><td>Kalrez</td><td>compound 7075; vendor: Marco Rubber</td></tr><tr><td>H&lt;sub&gt;2&lt;/sub&gt;S resistant elastomer o-rings</td><td>Marco Rubber</td><td>Markez</td><td>compound Z1028</td></tr><tr><td>H&lt;sub&gt;2&lt;/sub&gt;S resistant elastomer o-rings</td><td>Seals Eastern, Inc.</td><td>Aflas</td><td>vendor: Marco Rubber</td></tr></tbody></table>

making record-efficiency sns solar cells by thermal evaporation and atomic layer deposition

锡硫化物（SNS）是候选吸收材料对于地球丰富的，无毒的太阳能电池。 SnS的提供方便的相位控制和全等热蒸发的快速增长，而且吸收可见光强烈。然而，很长一段时间的SnS太阳能电池的创纪录的功率转换效率保持在2％以下。最近，我们证明了4.36％，采用SNS沉积通过原子层沉积的新纪录认证的效率，并采用热蒸发3.88％。这里对这些记录的太阳能电池的制造过程进行说明，并在制造过程中的统计分布的报道。在单个衬底上测量的效率的标准偏差是通常超过0.5％。所有步骤，包括衬底的选择和清洗，钼溅射后接触（阴极），SNS沉积，退火，表面钝化，锌（O，S）缓冲层的选择和沉积，透明导体（阳极）沉积和金属化描述。在每一基底我们制造11各个装置，每个有源区0.25厘米2。此外，对于电流 - 电压曲线之下模拟太阳光高吞吐量的测量，和外部量子效率的测量与可变轻偏压的系统进行说明。有了这个系统，我们能够测量以自动的方式在最短的时间内对所有11台设备完整的数据集。这些结果说明学习大样本组，而不是狭隘专注于最高性能的设备的价值。大型数据集帮助我们辨别和消除影响我们的设备单项损失的机制。

在图如上所述6-8的结果显示了两种具有代表性的"基线"TE生长样本。照射的J - V数据为这两个样品是绘制在图6中的第一样本（"SnS140203F"）得到该装置用的3.88％认证效率先前报道9代表合营分布也示每个样品。对于给定的偏置电压，这些分布被计算为<img alt="式（1）" src="/files/ftp_upload/52705/52705eq1.jpg" />其中&lt;J&gt;时是测量所有设?...

Watch this Scientific Journal Video about Making Record-efficiency SnS Solar Cells by Thermal Evaporation and Atomic Layer Deposition at JoVE.com

Making Record-efficiency SnS Solar Cells by Thermal Evaporation and Atomic Layer Deposition

Tin sulfide (SnS) is a candidate material for Earth-abundant, non-toxic solar cells. Here, we demonstrate the fabrication procedure of the SnS solar cells employing atomic layer deposition, which yields 4.36% certified power conversion efficiency, and thermal evaporation which yields 3.88%.

通过热蒸发和原子层沉积使记录效率的SnS太阳能电池

Tin sulfide (SnS) is a candidate absorber material for Earth-abundant, non-toxic solar cells. SnS offers easy phase control and rapid growth by congruent ...

making-record-efficiency-sns-solar-cells-thermal-evaporation-atomic

Universidad de Cartagena UDEC

Research

JoVE Journal

Engineering

42.7K 次观看.  Massachusetts Institute of Technology. Tin sulfide (SnS) is a candidate material for Earth-abundant, non-toxic solar cells. Here, we demonstrate the fabrication procedure of the SnS solar cells employing atomic layer deposition, which yields 4.36% certified power conversion efficiency, and thermal evaporation which yields 3.88%.

视频: Making Record-efficiency SnS Solar Cells by Thermal Evaporation and Atomic Layer Deposition

Polycrystalline Silicon Thin-film Solar cells with Plasmonic-enhanced Light-trapping

One of major approaches to cheaper solar cells is reducing the amount of semiconductor material used for their fabrication and making cells thinner. To compensate for lower light absorption such physically thin devices have to incorporate light-trapping which increases their optical thickness. Light scattering by textured surfaces is a common technique but it cannot be universally applied to all solar cell technologies. Some cells, for example those made of evaporated silicon, are planar as produced and they require an alternative light-trapping means suitable for planar devices. Metal nanoparticles formed on planar silicon cell surface and capable of light scattering due to surface plasmon resonance is an effective approach.
The paper presents a fabrication procedure of evaporated polycrystalline silicon solar cells with plasmonic light-trapping and demonstrates how the cell quantum efficiency improves due to presence of metal nanoparticles.
To fabricate the cells a film consisting of alternative boron and phosphorous doped silicon layers is deposited on glass substrate by electron beam evaporation. An Initially amorphous film is crystallised and electronic defects are mitigated by annealing and hydrogen passivation. Metal grid contacts are applied to the layers of opposite polarity to extract electricity generated by the cell. Typically, such a ~2 &mu;m thick cell has a short-circuit current density (Jsc) of 14-16 mA/cm2, which can be increased up to 17-18 mA/cm2 (~25% higher) after application of a simple diffuse back reflector made of a white paint.
To implement plasmonic light-trapping a silver nanoparticle array is formed on the metallised cell silicon surface. A precursor silver film is deposited on the cell by thermal evaporation and annealed at 23&deg;C to form silver nanoparticles. Nanoparticle size and coverage, which affect plasmonic light-scattering, can be tuned for enhanced cell performance by varying the precursor film thickness and its annealing conditions. An optimised nanoparticle array alone results in cell Jsc enhancement of about 28%, similar to the effect of the diffuse reflector. The photocurrent can be further increased by coating the nanoparticles by a low refractive index dielectric, like MgF2, and applying the diffused reflector. The complete plasmonic cell structure comprises the polycrystalline silicon film, a silver nanoparticle array, a layer of MgF2, and a diffuse reflector. The Jsc for such cell is 21-23 mA/cm2, up to 45% higher than Jsc of the original cell without light-trapping or ~25% higher than Jsc for the cell with the diffuse reflector only.
Introduction
Light-trapping in silicon solar cells is commonly achieved via light scattering at textured interfaces. Scattered light travels through a cell at oblique angles for a longer distance and when such angles exceed the critical angle at the cell interfaces the light is permanently trapped in the cell by total internal reflection (Animation 1: Light-trapping). Although this scheme works well for most solar cells, there are developing technologies where ultra-thin Si layers are produced planar (e.g. layer-transfer technologies and epitaxial c-Si layers) 1 and or when such layers are not compatible with textures substrates (e.g. evaporated silicon) 2. For such originally planar Si layer alternative light trapping approaches, such as diffuse white paint reflector 3, silicon plasma texturing 4 or high refractive index nanoparticle reflector 5 have been suggested.
Metal nanoparticles can effectively scatter incident light into a higher refractive index material, like silicon, due to the surface plasmon resonance effect 6. They also can be easily formed on the planar silicon cell surface thus offering a light-trapping approach alternative to texturing. For a nanoparticle located at the air-silicon interface the scattered light fraction coupled into silicon exceeds 95% and a large faction of that light is scattered at angles above critical providing nearly ideal light-trapping condition (Animation 2: Plasmons on NP). The resonance can be tuned to the wavelength region, which is most important for a particular cell material and design, by varying the nanoparticle average size, surface coverage and local dielectric environment 6,7. Theoretical design principles of plasmonic nanoparticle solar cells have been suggested 8. In practice, Ag nanoparticle array is an ideal light-trapping partner for poly-Si thin-film solar cells because most of these design principle are naturally met. The simplest way of forming nanoparticles by thermal annealing of a thin precursor Ag film results in a random array with a relatively wide size and shape distribution, which is particularly suitable for light-trapping because such an array has a wide resonance peak, covering the wavelength range of 700-900 nm, important for poly-Si solar cell performance. The nanoparticle array can only be located on the rear poly-Si cell surface thus avoiding destructive interference between incident and scattered light which occurs for front-located nanoparticles 9. Moreover, poly-Si thin-film cells do not requires a passivating layer and the flat base-shaped nanoparticles (that naturally result from thermal annealing of a metal film) can be directly placed on silicon further increases plasmonic scattering efficiency due to surface plasmon-polariton resonance 10.
The cell with the plasmonic nanoparticle array as described above can have a photocurrent about 28% higher than the original cell. However, the array still transmits a significant amount of light which escapes through the rear of the cell and does not contribute into the current. This loss can be mitigated by adding a rear reflector to allow catching transmitted light and re-directing it back to the cell. Providing sufficient distance between the reflector and the nanoparticles (a few hundred nanometers) the reflected light will then experience one more plasmonic scattering event while passing through the nanoparticle array on re-entering the cell and the reflector itself can be made diffuse - both effects further facilitating light scattering and hence light-trapping. Importantly, the Ag nanoparticles have to be encapsulated with an inert and low refractive index dielectric, like MgF2 or SiO2, from the rear reflector to avoid mechanical and chemical damage 7. Low refractive index for this cladding layer is required to maintain a high coupling fraction into silicon and larger scattering angles, which are ensured by the high optical contrast between the media on both sides of the nanoparticle, silicon and dielectric 6. The photocurrent of the plasmonic cell with the diffuse rear reflector can be up to 45% higher than the current of the original cell or up to 25% higher than the current of an equivalent cell with the diffuse reflector only.

Polycrystalline silicon thin-film solar cells on glass are fabricated by deposition of boron and phosphorous doped silicon layers followed by crystallisation, defect passivation and metallisation. Plasmonic light-trapping is introduced by forming Ag nanoparticles on the silicon cell surface capped with a diffused reflector resulting in ~45% photocurrent enhancement.

多晶硅薄膜太阳能电池电浆增强光捕获

One of major approaches to cheaper solar cells is reducing the amount of semiconductor material used for their fabrication and making cells thinner. To ...

科研

工程学

Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO

Atmospheric pressure spatial atomic layer deposition (AP-SALD) was used to deposit n-type ZnO and Zn1-xMgxO thin films onto p-type thermally oxidized Cu2O substrates outside vacuum at low temperature. The performance of photovoltaic devices featuring atmospherically fabricated ZnO/Cu2O heterojunction was dependent on the conditions of AP-SALD film deposition, namely, the substrate temperature and deposition time, as well as on the Cu2O substrate exposure to oxidizing agents prior to and during the ZnO deposition. Superficial Cu2O to CuO oxidation was identified as a limiting factor to heterojunction quality due to recombination at the ZnO/Cu2O interface. Optimization of AP-SALD conditions as well as keeping Cu2O away from air and moisture in order to minimize Cu2O surface oxidation led to improved device performance. A three-fold increase in the open-circuit voltage (up to 0.65 V) and a two-fold increase in the short-circuit current density produced solar cells with a record 2.2% power conversion efficiency (PCE). This PCE is the highest reported for a Zn1-xMgxO/Cu2O heterojunction formed outside vacuum, which highlights atmospheric pressure spatial ALD as a promising technique for inexpensive and scalable fabrication of Cu2O-based photovoltaics.

Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO

Here we present a protocol for synthesizing Zn1-xMgxO/Cu2O heterojunctions in open-air at low temperature via atmospheric pressure spatial atomic layer deposition (AP-SALD) of Zn1-xMgxO on cuprous oxide. Such high quality conformal metal oxides can be grown on a variety of substrates including plastics by this cheap and scalable method.

在铜改善异质结质量<sub&gt; 2</sub&gt; O型的太阳能电池通过大气压力的空间原子层沉积的优化<br /&gt;锌<sub&gt; 1-X</sub&gt;镁<sub系列&gt; X</sub&gt; 0

Atmospheric pressure spatial atomic layer deposition (AP-SALD) was used to deposit n-type ZnO and Zn1-xMgxO thin films onto p-type thermally oxidized Cu2O ...

化学

Integration of Light Trapping Silver Nanostructures in Hydrogenated Microcrystalline Silicon Solar Cells by Transfer Printing

One of the potential applications of metal nanostructures is light trapping in solar cells, where unique optical properties of nanosized metals, commonly known as plasmonic effects, play an important role. Research in this field has, however, been impeded owing to the difficulty of fabricating devices containing the desired functional metal nanostructures. In order to provide a viable strategy to this issue, we herein show a transfer printing-based approach that allows the quick and low-cost integration of designed metal nanostructures with a variety of device architectures, including solar cells. Nanopillar poly(dimethylsiloxane) (PDMS) stamps were fabricated from a commercially available nanohole plastic film as a master mold. On this nanopatterned PDMS stamps, Ag films were deposited, which were then transfer-printed onto block copolymer (binding layer)-coated hydrogenated microcrystalline Si (&#181;c-Si:H) surface to afford ordered Ag nanodisk structures. It was confirmed that the resulting Ag nanodisk-incorporated &#181;c-Si:H solar cells show higher performances compared to a cell without the transfer-printed Ag nanodisks, thanks to plasmonic light trapping effect derived from the Ag nanodisks. Because of the simplicity and versatility, further device application would also be feasible thorough this approach.

A viable transfer printing-based methodology to introduce plasmonic metal nanostructures in solar cells is described. Using nanopillar poly(dimethylsiloxane) stamps, an Ag-based ordered nanodisk array was integrated with standard hydrogenated microcrystalline Si solar cells, which led to improved device performances due to plasmonic light trapping.

灯光诱杀银纳米结构通过转移印花在氢化微晶硅太阳能电池集成

One of the potential applications of metal nanostructures is light trapping in solar cells, where unique optical properties of nanosized metals, commonly ...

Printing Fabrication of Bulk Heterojunction Solar Cells and In Situ Morphology Characterization

Polymer-based materials hold promise as low-cost, flexible efficient photovoltaic devices. Most laboratory efforts to achieve high performance devices have used devices prepared by spin coating, a process that is not amenable to large-scale fabrication. This mismatch in device fabrication makes it difficult to translate quantitative results obtained in the laboratory to the commercial level, making optimization difficult. Using a mini-slot die coater, this mismatch can be resolved by translating the commercial process to the laboratory and characterizing the structure formation in the active layer of the device in real time and in situ as films are coated onto a substrate. The evolution of the morphology was characterized under different conditions, allowing us to propose a mechanism by which the structures form and grow. This mini-slot die coater offers a simple, convenient, material efficient route by which the morphology in the active layer can be optimized under industrially relevant conditions. The goal of this protocol is to show experimental details of how a solar cell device is fabricated using a mini-slot die coater and technical details of running in situ structure characterization using the mini-slot die coater.

Printing Fabrication of Bulk Heterojunction Solar Cells and In Situ Morphology Characterization

Here, we present a protocol to fabricate organic thin film solar cells using a mini-slot die coater and related in-line structure characterizations using synchrotron scattering techniques.

散装异质结太阳能电池的印刷和制作<em&gt;原位</em&gt;形态特征

Polymer-based materials hold promise as low-cost, flexible efficient photovoltaic devices. Most laboratory efforts to achieve high performance devices ...

Fabrication of Fully Solution Processed Inorganic Nanocrystal Photovoltaic Devices

We demonstrate a method for the preparation of fully solution processed inorganic solar cells from a spin and spray coating deposition of nanocrystal inks. For the photoactive absorber layer, colloidal CdTe and CdSe nanocrystals (3-5 nm) are synthesized using an inert hot injection technique and cleaned with precipitations to remove excess starting reagents. Similarly, gold nanocrystals (3-5 nm) are synthesized under ambient conditions and dissolved in organic solvents. In addition, precursor solutions for transparent conductive indium tin oxide (ITO) films are prepared from solutions of indium and tin salts paired with a reactive oxidizer. Layer-by-layer, these solutions are deposited onto a glass substrate following annealing (200-400 &#176;C) to build the nanocrystal solar cell (glass/ITO/CdSe/CdTe/Au). Pre-annealing ligand exchange is required for CdSe and CdTe nanocrystals where films are dipped in NH4Cl:methanol to replace long-chain native ligands with small inorganic Cl- anions. NH4Cl(s) was found to act as a catalyst for the sintering reaction (as a non-toxic alternative to the conventional CdCl2(s) treatment) leading to grain growth (136&#177;39 nm) during heating. The thickness and roughness of the prepared films are characterized with SEM and optical profilometry. FTIR is used to determine the degree of ligand exchange prior to sintering, and XRD is used to verify the crystallinity and phase of each material. UV/Vis spectra show high visible light transmission through the ITO layer and a red shift in the absorbance of the cadmium chalcogenide nanocrystals after thermal annealing. Current-voltage curves of completed devices are measured under simulated one sun illumination. Small differences in deposition techniques and reagents employed during ligand exchange have been shown to have a profound influence on the device properties. Here, we examine the effects of chemical (sintering and ligand exchange agents) and physical treatments (solution concentration, spray-pressure, annealing time and annealing temperature) on photovoltaic device performance.

This protocol describes the synthesis and solution deposition of inorganic nanocrystals layer by layer to produce thin film electronics on non-conductive surfaces. Solvent-stabilized inks can produce complete photovoltaic devices on glass substrates via spin and spray coating following post-deposition ligand exchange and sintering.

全面解决方案处理的无机纳米晶体光伏器件的制造

We demonstrate a method for the preparation of fully solution processed inorganic solar cells from a spin and spray coating deposition of nanocrystal ...

Influence of Hybrid Perovskite Fabrication Methods on Film Formation, Electronic Structure, and Solar Cell Performance

Hybrid organic/inorganic halide perovskites have lately been a topic of great interest in the field of solar cell applications, with the potential to achieve device efficiencies exceeding other thin film device technologies. Yet, large variations in device efficiency and basic physical properties are reported. This is due to unintentional variations during film processing, which have not been sufficiently investigated so far. We therefore conducted an extensive study of the morphology and electronic structure of a large number of CH3NH3PbI3 perovskite where we show how the preparation method as well as the mixing ratio of educts methylammonium iodide and lead(II) iodide impact properties like film formation, crystal structure, density of states, energy levels, and ultimately the solar cell performance.

We present an extensive study on the effects of different fabrication methods for organic/inorganic perovskite thin films by comparing crystal structures, density of states, energy levels, and ultimately the solar cell performance.

上成膜钙钛矿型混合制造方法，电子结构和太阳能电池性能的影响

Hybrid organic/inorganic halide perovskites have lately been a topic of great interest in the field of solar cell applications, with the potential to ...

Morphology Control for Fully Printable Organic&#8211;Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer

The photoactive layer of a typical organic thin-film bulk-heterojunction (BHJ) solar cell commonly uses fullerene derivatives as the electron-accepting material. However, fullerene derivatives are air-sensitive; therefore, air-stable material is needed as an alternative. In the present study, we propose and describe the properties of Ti-alkoxide as an alternative electron-accepting material to fullerene derivatives to create highly air-stable BHJ solar cells. It is well-known that controlling the morphology in the photoactive layer, which is constructed with fullerene derivatives as the electron acceptor, is important for obtaining a high overall efficiency through the solvent method. The conventional solvent method is useful for high-solubility materials, such as fullerene derivatives. However, for Ti-alkoxides, the conventional solvent method is insufficient, because they only dissolve in specific solvents. Here, we demonstrate a new approach to morphology control that uses the molecular bulkiness of Ti-alkoxides without the conventional solvent method. That is, this method is one approach to obtain highly efficient, air-stable, organic-inorganic bulk-heterojunction solar cells.

A method for fully printable, fullerene-free, highly air-stable, bulk-heterojunction solar cells based on Ti alkoxides as the electron acceptor and the electron-donating polymer fabrication is described here. Moreover, a method for controlling the morphology of the photoactive layer through the molecular bulkiness of the Ti-alkoxide units is reported.

基于一个钛醇盐和半导体聚合物为全可印刷有机 - 无机批量异质结太阳能电池形貌控制

The photoactive layer of a typical organic thin-film bulk-heterojunction (BHJ) solar cell commonly uses fullerene derivatives as the electron-accepting ...

Well-aligned Vertically Oriented ZnO Nanorod Arrays and their Application in Inverted Small Molecule Solar Cells

This manuscript describes how to design and fabricate efficient inverted solar cells, which are based on a two-dimensional conjugated small molecule (SMPV1) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), by utilizing ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The inverted SMPV1:PC71BM solar cells with ZnO NRs that grew on both a sputtered and sol-gel processed AZO seed layer are fabricated. Compared with the AZO thin film prepared by the sol-gel method, the sputtered AZO thin film exhibits better crystallization and lower surface roughness, according to X-ray diffraction (XRD) and atomic force microscope (AFM) measurements. The orientation of the ZnO NRs grown on a sputtered AZO seed layer shows better vertical alignment, which is beneficial for the deposition of the subsequent active layer, forming better surface morphologies. Generally, the surface morphology of the active layer mainly dominates the fill factor (FF) of the devices. Consequently, the well-aligned ZnO NRs can be used to improve the carrier collection of the active layer and to increase the FF of the solar cells. Moreover, as an anti-reflection structure, it can also be utilized to enhance the light harvesting of the absorption layer, with the power conversion efficiency (PCE) of solar cells reaching 6.01%, higher than the sol-gel based solar cells with an efficiency of 4.74%.

This manuscript describes how to design and fabricate efficient inverted SMPV1:PC71BM solar cells with ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The well-aligned vertically oriented ZnO NRs exhibit high crystalline properties. The power conversion efficiency of solar cells can reach 6.01%.

定向定向 ZnO 纳米阵列及其在倒小分子太阳电池中的应用

This manuscript describes how to design and fabricate efficient inverted solar cells, which are based on a two-dimensional conjugated small molecule ...

Flash Infrared Annealing for Perovskite Solar Cell Processing

Organic&#8211;inorganic perovskites have an impressive potential for the design of next generation solar cells and are currently considered for upscaling and commercialization. Currently, perovskite solar cells rely on spin-coating which is neither practical for large areas nor environmentally friendly. Indeed, one of the conventional and most effective lab-scale methods to induce perovskite crystallization, the antisolvent method, requires an amount of toxic solvent that is difficult to apply on larger surfaces. To solve this problem, an antisolvent-free and rapid thermal annealing process called flash infrared annealing (FIRA) can be used to produce highly crystalline perovskite films. The FIRA oven is composed of an array of near-infrared halogen lamps with an illumination power of 3,000 kW/m2. A hollow aluminum body enables an effective water-cooling system. The FIRA method allows the synthesis of perovskite films in less than 2 s, achieving efficiencies &#62;20%. FIRA has a unique potential for the industry because it can be adapted to continuous processing, is antisolvent-free, and does not require lengthy, hour-long annealing steps.

We describe a flash infrared annealing method used for the synthesis of perovskite and mesoscopic-TiO2 films. Annealing parameters are varied and optimized for processing on fluorine-doped tin oxide (FTO) glass and indium tin oxide-coated polyethylene terephthalate (ITO PET), subsequently giving devices power conversion efficiencies &#62;20%.

用于佩罗夫斯基特太阳能电池处理的闪光红外退火

Organic&#8211;inorganic perovskites have an impressive potential for the design of next generation solar cells and are currently considered for upscaling ...

环境科学

Close-Space Sublimation-Deposited Ultra-Thin CdSeTe/CdTe Solar Cells for Enhanced Short-Circuit Current Density and Photoluminescence

Developments in photovoltaic device architectures are necessary to make solar energy a cost-effective and reliable source of renewable energy amidst growing global energy demands and climate change. Thin film CdTe technology has demonstrated cost-competitiveness and increasing efficiencies due partially to rapid fabrication times, minimal material usage, and introduction of a CdSeTe alloy into a ~3 &#956;m absorber layer. This work presents the close-space sublimation fabrication of thin, 1.5 &#181;m CdSeTe/CdTe bilayer devices using an automated in-line vacuum deposition system. The thin bilayer structure and fabrication technique minimize deposition time, increase device efficiency, and facilitate future thin absorber-based device architecture development. Three fabrication parameters appear to be the most impactful for optimizing thin CdSeTe/CdTe absorber devices: substrate preheat temperature, CdSeTe:CdTe thickness ratio, and CdCl2 passivation. For proper sublimation of the CdSeTe, the substrate temperature prior to deposition must be ~540 &#176;C (higher than that for CdTe) as controlled by dwell time in a preheat source. Variation in the CdSeTe:CdTe thickness ratio reveals a strong dependence of device performance on this ratio. The optimal absorber thicknesses are 0.5 &#956;m CdSeTe/1.0 &#956;m CdTe, and non-optimized thickness ratios reduce efficiency through back-barrier effects. Thin absorbers are sensitive to CdCl2 passivation variation; a much less aggressive CdCl2 treatment (compared to thicker absorbers) regarding both temperature and time yields optimal device performance. With optimized fabrication conditions, CdSeTe/CdTe increases device short-circuit current density and photoluminescence intensity compared to single-absorber CdTe. Additionally, an in-line close-space sublimation vacuum deposition system offers material and time reduction, scalability, and attainability of future ultra-thin absorber architectures.

This work describes the complete fabrication process of thin absorber cadmium selenium telluride/cadmium telluride photovoltaic devices for enhanced efficiency. The process utilizes an automated in-line vacuum system for close-space sublimation deposition that is scalable, from fabrication of small area research devices as well as large-scale modules.

近空间升升-沉积超薄CDSeTe/CdTe太阳能电池，增强短路电流密度和光致发光

Developments in photovoltaic device architectures are necessary to make solar energy a cost-effective and reliable source of renewable energy amidst ...

通过热蒸发和原子层沉积使记录效率的SnS太阳能电池

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