在本研究中，我們利用噴塗沉積法製作ZnO/Cu-In-Zn-S及CIS/ITO p-n junction兩種不同的異質結構薄膜。第一部分的研究中，我們提出利用噴塗法製作複合薄膜的方式，將不同重量的Cu-In-Zn-S (CIZS)粉體與不同體積的ZnO混合，以此製作出各種不同比例的複合式薄膜，並用在光電化學水分解產氫的實驗中。CIZS在此被當作吸光材料，而ZnO作為電荷傳輸的路徑，在後續的電化學實驗中，我們發現CIZS粉體的分布對於PEC活性有相當大的影響，使用小顆粒的CIZS粉體時(0.56 μm)，可獲得較高的光電流密度，且在連續5小時的產氫實驗中可收集到3.27 μmol/ cm2 的產氫量。 後續的電化學實驗中，我們利用電化學阻抗頻譜(EIS)來分析複合薄膜的電荷轉移機制。此外，在複合薄膜外側的ZnO除了當作黏著劑之外，也同時作為複合薄膜的保護層。在所有的PEC實驗中，我們皆使用0.5 M K2SO4作為此實驗的電解質，並未使用犧牲試劑。穩定性測試的實驗中，在外加偏壓0.2 V vs. SCE的條件下，經過一小時的照光實驗後，此複合薄膜仍具有75.67%的反應效率。 第二部分的研究中，我們利用相同的噴塗法並改變前驅物比例，製作出不同性質的Cu-In-S(CIS)薄膜半導體，並利用p-type CIS與不同功函數的n-type ITO製作出CIS/ITO p-n junction薄膜半導體，與單純的CIS p-type薄膜電極相比，效率最高的CIS/ITO p-n junction薄膜電極的光電流密度大約是CIS p-type薄膜電極的兩倍，所以在後續的電化學實驗中，我們也嘗試用不同方法來討論造成其結果的原因。 本研究證明了噴塗法是種簡單且低成本的複合薄膜製作方式，除了可以將粉體噴在各種不同的半導體中，也可以簡單的改變噴塗前驅物的比例來製作不同性質的薄膜半導體。 ;In this research, we prepared ZnO/Cu-In-Zn-S and CIS/ITO p-n junction heterogeneous structure thin films by using sprayed deposition method. In the first part, we present a sprayed composite thin film, comprising Cu-In-Zn-S (CIZS) particles embedded in ZnO matrix for photoelectrochemical hydrogen production from water splitting. CIZS, a photoactive semiconductor was used as a photon absorber, whereas ZnO channels as the pathway for charge transfer. It was found that the distribution of the CIZS particles had a direct impact on the PEC activity. A more homogeneous dispersion of smaller CIZS particles (0.56 μm) within ZnO matrix exhibited a higher photocurrent density, and 3.27 μmol/ cm2 hydrogen evolution for 5 h. Electrochemical impedance spectroscopy (EIS) was employed to analyze the charge transfer mechanism of this composite thin film. In addition, ZnO coating on top of CIZS particles also served as the adhesion and protection layers. All the PEC experiments were performed in 0.5 M K2SO4 electrolyte. No sacrificial reagents were used. The composite electrode was stable under illumination: 75.67% of photo-activity remained after 1 h illumination at a bias of 0.2 V vs. SCE. In the second part, we changed the ratio of precursor solution to prepare the different type of Cu-In-S (CIS) thin film semiconductors by the same method. In addition, the CIS p-type thin film is combined with ITO of high and low work function to produce CIS/ITO p-n junction thin film semiconductor. The photocurrent density of CIS/ITO p-n junction thin film compare favorably with CIS p-type thin film, and the current density of the most efficient CIS/ITO p-n junction thin film is about twice as much as the CIS p-type thin film. Therefore, we discussed the reason by using different method in the follow-up PEC test. This study demonstrates a simple and low-cost spray preparation of composite thin film consisting of particles embedded in any semiconductor matrix, and easy to change the ratio of precursor solution to make various thin film semiconductors.
