以高壓水熱法製作銅鋅錫硫化物(Cu2ZnSnS4)粉體的研究

The study on producing copper-zinc-tin-sulfur (Cu2ZnSnS4, CZTS) powders by using high pressure hydrothermal method

戴子淳(Zih-Chun Dai)

指導教授 ： 黃景良

崑山科技大學/工程學院/機械工程研究所/碩士(2012年)

摘要

CIGS材料所使用的In及Ga材料其地球蘊藏量較少，In及Ga材料與IC產業相爭，且硒化製程中的硒化氫 (H2Se)氣體有毒，近年研究出可替代的吸收層材料，例如：銅鋅錫硫化合物 (Cu2ZnSnS4，簡稱CZTS)、銅鋅錫硒化合物 (Cu2ZnSnSe4，簡稱CZTSe) 及其他似黃銅礦結構的四元化合物半導體。CZTS為取代CIGS當吸收層製程與特性研究資料有限，本實驗利用不同方式來製備CZTS粉末。此研究使用高壓水熱法製作Cu2ZnSnS4(CZTS)粉體。在不同反應時間下，改變多種可控制條件，例如反應物種類、高壓水熱法反應時間、反應物濃度等，從中探討取得最佳合成條件。製備生成的粉末以XRD、SEM、UV-Vis分析其特性。在反應物種類中，金屬元素來自於CuCl、CuCl2、SnCl2.2H2O、SnSO4.2H2O、ZnCl2，元素硫來自硫。因此探討出合適的合成反應物：為CuCl、SnCl2.2H2O、ZnCl2、硫脲。高壓水熱法反應時間方面，經實驗研究出適合的時間48小時以上，較能減少二元相或三元相產物生成。針對硫脲的濃度研究裡，為避免硫脲與銅離子在反應溶液中產生錯合物，硫脲的當量濃度須比銅離子大四倍，綜合以上條件即可得到符合JCPDS Card的單晶相、能隙約為1.45eV的Cu2ZnSnS4粉體。

關鍵字

粉體 ； CZTS

並列摘要

Owing to the limited hidden volume of In and Ga material which are used to fabricate the CIGS, the shortage of those materials may occur. Meanwhile, H2Se used in selenide process (one of CIGS processes) is toxic gas. Therefore, in recent years there are some alternative absorption layer materials substituting CIGS, such as copper-zinc-tin-sulfur compounds (Cu2ZnSnS4, referred to CZTS), copper-zinc-tin-selenium compounds (Cu2ZnSnSe4, referred to CZTSe) and other like quaternary compound semiconductors in the chalcopyrite structure. In this study, high pressure hydrothermal method is used to produce Cu2ZnSnS4 (CZTS) powder. From the different conditions for different species of reactants, reaction time of the high-pressure hydrothermal method and the reactant concentration, the optimal synthesis conditions can be found out. The characteristics of prepared powders are analyzed by XRD, SEM, UV-Vis analysis. Metal elements of Cu2ZnSnS4 are obtained from the reactive species CuCl, CuCl2, SnCl2.2H2O, SnSO4.2H2O and ZnCl2. And the sulfur element is obtained from thiourea. In this study, the most appropriate synthesis reactants CuCl, SnCl2.2H2O, ZnCl2, and thiourea are adopted. The suitable high-pressure hydrothermal reaction time is found out from experiments should be more than 48 hours, the binary phase or ternary phase product formation then can be reduced. In order to avoid the complexes are produced in the thiourea and copper ions in the reaction solution, thiourea concentration should be four times greater than copper ions. The single crystal phase of Cu2ZnSnS4 powder with about 1.45eV energy gap in accordance with the JCPDS Card can be obtained from the above conditions.

並列關鍵字

powders ； CZTS

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