Photovoltaic materials: Cu2ZnSnS4(CZTS) nanocrystals synthesized via industrially scalable, green, one‐step mechanochemical process

Balá? Peter; Hegedus Michal; Balá? Matej; Daneu Nina; Siffalovic Peter; Bujňáková Zdenka; Tóthová Erika; Te?ínsky Matej; Achimovi?ová Marcela; Brian?in Jaroslav; Dutková Erika; Kaňuchová Mária; Fabián Martin; Kitazono Satoshi; Dobrozhan Oleksandr

摘要

Abstract > The present study demonstrates a scalable approach towards the pure Cu <sub>2</sub> ZnSnS <sub>4</sub> (CZTS) phase starting from microsized Cu, Zn, Sn, and S mixture or a combination of nanosized CuS, SnS plus microsized Zn and S. A set of mechanochemical reactions was carried out in an industrial vibratory mill. The pure CZTS phase was obtained after 360?minutes of milling with an average crystallite size of 15?nm for both mixtures. The kinetics of CZTS formation was investigated following the X‐ray diffractometry (XRD) patterns of the reaction mixtures milled for various times. The morphology of particles and their elemental composition was studied by scanning electron microscopy (SEM)/transmission electron spectroscopy (TEM) and EDX analysis. Photoelectron spectroscopy (XPS) analysis showed the presence of Cu + , Zn 2+ , Sn 4+ , and S 2? species on the surface of CZTS with only minor oxidation. Thermal stability of the synthesized materials was followed by thermogravimetric analysis. Based on UV‐VIS measurements, the calculated bandgap E <sub> g </sub> ?=?1.44 to 1.50?eV of the synthesized CZTS samples is acceptable for photovoltaic application. Moreover, the applied mechanochemical approach can produce 100 to 500?g of CZTS in a batch mode experiment that is 10 to 50 times higher amount as the throughput of laboratory planetary mills. Hypothetically, in the applied industrial eccentric vibratory mill, the amount can be increased up to 50?kg per one batch. </abstract> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> <div class="translation abstracttxt"> <span class="zhankaihshouqi fivelineshidden" id="abstract"> <span>机译：</span><Abstract Type =“Main”XML：Lang =“en”> <标题类型=“main”>抽象</ title> > 本研究证明了纯粹铜的可扩展方法 <sub> 2 </ sub> znsns. <sub> 4 </ sub> （CZT）从微黄铜，Zn，Sn和S混合物或纳米型CU，Sn的组合开始，在工业振动磨机中进行一组机械化反应。在360℃的碾磨后得到纯CZTS相，对于两种混合物，平均微晶尺寸为15Ω·Nm。在X射线衍射术（XRD）图案磨削各次的反应混合物的X射线衍射术（XRD）图案之后研究了CZTS形成的动力学。通过扫描电子显微镜（SEM）/透射电子光谱（TEM）和EDX分析，研究了颗粒的形态及其元素组合物。光电子体光谱（XPS）分析显示CU的存在 + </ sup> ，Zn. 2 + </ sup> ，sn. 4 + </ sup> 和S. 2？</ sup> 只有轻微氧化的CZTS表面上的物种。接下来是合成材料的热稳定性，热重分析。基于UV-VI测量，计算的带隙 e </ i> <sub> g </ i> </ sub> ？=？1.44至1.50？合成的CZTS样品的EV对于光伏应用是可接受的。此外，所应用的机械化学方法可以在批量模式实验中产生100至500μg的CZT，其量的吞吐量较高的10至50倍，作为实验室行星磨机的吞吐量。假设，在施加的工业偏心振动磨机中，每批批量可以增加50Ω千克。 </ p> </摘要> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> </div> <div class="record"> <h2 class="all_title" id="enpatent33" >著录项</h2> <ul> <li> <span class="lefttit">来源</span> <div style="width: 86%;vertical-align: text-top;display: inline-block;"> <a href='/journal-foreign-29870/'>《Progress in photovoltaics》</a> <b style="margin: 0 2px;">|</b><span>2019年第9期</span><b style="margin: 0 2px;">|</b><span>共14页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Balá? Peter&option=202" target="_blank" rel="nofollow">Balá? Peter;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Hegedus Michal&option=202" target="_blank" rel="nofollow">Hegedus Michal;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Balá? Matej&option=202" target="_blank" rel="nofollow">Balá? Matej;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Daneu Nina&option=202" target="_blank" rel="nofollow">Daneu Nina;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Siffalovic Peter&option=202" target="_blank" rel="nofollow">Siffalovic Peter;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Bujňáková Zdenka&option=202" target="_blank" rel="nofollow">Bujňáková Zdenka;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Tóthová Erika&option=202" target="_blank" rel="nofollow">Tóthová Erika;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Te?ínsky Matej&option=202" target="_blank" rel="nofollow">Te?ínsky Matej;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Achimovi?ová Marcela&option=202" target="_blank" rel="nofollow">Achimovi?ová Marcela;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Brian?in Jaroslav&option=202" target="_blank" rel="nofollow">Brian?in Jaroslav;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Dutková Erika&option=202" target="_blank" rel="nofollow">Dutková Erika;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Kaňuchová Mária&option=202" target="_blank" rel="nofollow">Kaňuchová Mária;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Fabián Martin&option=202" target="_blank" rel="nofollow">Fabián Martin;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Kitazono Satoshi&option=202" target="_blank" rel="nofollow">Kitazono Satoshi;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Dobrozhan Oleksandr&option=202" target="_blank" rel="nofollow">Dobrozhan Oleksandr;</a> </p> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zkzz" style="display: none;">展开▼</span> </div> </li> <li> <div style="display: flex;"> <span class="lefttit">作者单位</span> <div style="position: relative;margin-left: 3px;max-width: 639px;"> <div class="threelineshidden zhankaihshouqi" id="fOrgthree"> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>GEOtesta.s. ?mahova 1244/112 62700 Brno Czech Republic;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Jozef Stefan InstituteJamova cesta 39 S1‐1000 Ljublana Slovenia;</p> <p>Institute of PhysicsSlovak Academy of SciencesDúbravská cesta 9 845 11 Bratislava Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Institute of Earth Resources Faculty of Mining Ecology Process Control and GeotechnologiesTechnical University in Ko?iceLetná 9 04001 Ko?ice Slovakia;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> <p>Nihon Seiko Co. Ltd.1198 Yoshii Yabu‐shi Hyogo 667‐1111 Japan;</p> <p>Institute of GeotechnicsSlovak Academy of SciencesWatsonova 45 04001 Ko?ice Slovakia;</p> </div> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zhdw" style="display: none;">展开▼</span> </div> </div> </li> <li > <span class="lefttit">收录信息</span> <span style="width: 86%;vertical-align: text-top;display: inline-block;"></span> </li> <li> <span class="lefttit">原文格式</span> <span>PDF</span> </li> <li> <span class="lefttit">正文语种</span> <span>eng</span> </li> <li> <span class="lefttit">中图分类</span> <span><a href="https://www.zhangqiaokeyan.com/clc/7667.html" title="通信系统（传输系统）">通信系统（传输系统）;</a><a href="https://www.zhangqiaokeyan.com/clc/1790.html" title="光电子技术、激光技术">光电子技术、激光技术;</a></span> </li> <li class="antistop"> <span class="lefttit">关键词</span> <p style="width: 86%;vertical-align: text-top;"> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Cu 2 ZnSnS 4&option=203" rel="nofollow">Cu 2 ZnSnS 4;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=CZTS&option=203" rel="nofollow">CZTS;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=green synthesis&option=203" rel="nofollow">green synthesis;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=industrial&option=203" rel="nofollow">industrial;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=mechanochemistry&option=203" rel="nofollow">mechanochemistry;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=photovoltaics&option=203" rel="nofollow">photovoltaics;</a> </p> <div class="translation"> 机译：Cu 2 ZnSns 4;CZTS;绿色合成;工业;技能;光伏; </div> </li> </ul> </div> </div> <div class="literature cardcommon"> <div class="similarity "> <h3 class="all_title" id="enpatent66">相似文献</h3> <div class="similaritytab clearfix"> <ul> <li class="active" >外文文献</li> <li >中文文献</li> <li >专利</li> </ul> </div> <div class="similarity_details"> <ul > <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/journal-foreign-detail/0704024604666.html">Photovoltaic materials: Cu2ZnSnS4(CZTS) nanocrystals synthesized via industrially scalable, green, one‐step mechanochemical process</a> <b>[J]</b> . <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Balá? 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href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=闰明涛&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,闰明涛</a> <span> <a href="/conference-cn-40083/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 2015年高校化学化工课程教学系列报告会 </a> <span> <span> . 2015</span> </span> </div> </li> <li> <div> <b>7. </b><a class="enjiyixqcontent" href="/academic-degree-domestic_mphd_thesis/020313317841.html">软脆碲镉汞晶体绿色环保化学机械抛光研究</a> <b>[A] </b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=宋亚星&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 宋亚星</a> <span> . 2014</span> </span> </div> </li> </ul> <ul style="display: none;"> <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/patent-detail/06120105100284.html">超微细晶体层生成方法、具有利用该超微细晶体层生成方法生成的超微细晶体层的机械部件、制造该机械部件的机械部件制造方法、及纳米晶体层生成方法、具有利用该纳米晶体层生成方法生成的纳米晶体层的机械部件、制造该机械部件的机械部件制造方法</a> <b>[P]</b> . <span> 中国专利： CN1905986A </span> <span> . 2007-01-31</span> </div> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/patent-detail/06120112060019.html">一步法在非晶体纳米材料上负载金属纳米晶的方法</a> <b>[P]</b> . <span> 中国专利： CN112044431A </span> <span> . 2020-12-08</span> </div> </li> <li> <div> <b>3. </b><a class="enjiyixqcontent" href="/patent-detail/06130409588402.html">Greener process to synthesize water-soluble Mn<Sup>2+</Sup>-doped CdSSe(ZnS) core(shell) nanocrystals for ratiometric temperature sensing, nanocrystals, and methods implementing nanocrystals</a> <b>[P]</b> . <span> 外国专利：  US9696317B2 </span> <span> . 2017-07-04</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：用于比例温度感测的水溶性Mn <Sup> 2 + </ Sup>掺杂CdSSe（ZnS）核（壳）纳米晶体的更绿色合成方法，纳米晶体和实现纳米晶体的方法 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130418328753.html">NEW AND GREENER PROCESS TO SYNTHESIZE WATER-SOLUBLE MN2+-DOPED CDSSE(ZNS) CORE(SHELL) NANOCRYSTALS FOR RATIOMETRIC TEMPERATURE SENSING, NANOCRYSTALS, AND METHODS IMPLEMENTING NANOCRYSTALS</a> <b>[P]</b> . <span> 外国专利：  US2014242631A1 </span> <span> . 2014-08-28</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：合成水溶性的MN2 +掺杂的CDSSE（ZNS）核（壳）纳米晶体的新方法和更绿色的过程，用于比率温度感测，纳米晶体和实现纳米晶体的方法 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130419828874.html">NEW AND GREENER PROCESS TO SYNTHESIZE WATER-SOLUBLE MN<Sup>2+</Sup>-DOPED CDSSE(ZNS) CORE(SHELL) NANOCRYSTALS FOR RATIOMETRIC TEMPERATURE SENSING, NANOCRYSTALS, AND METHODS IMPLEMENTING NANOCRYSTALS</a> <b>[P]</b> . <span> 外国专利：  WO2013066630A1 </span> <span> . 2013-05-10</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> 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