Deb Anjan, Vihervaara Anton, Popov Georgi, Chundak Mykhailo, Abdelaal Ahmed O, Santos Hugo L S, Heikkilä Mikko J, Kemell Marianna, Camargo Pedro H C, Ritala Mikko, Putkonen Matti
Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland.
ACS Omega. 2025 Apr 5;10(14):14522-14535. doi: 10.1021/acsomega.5c01360. eCollection 2025 Apr 15.
Hematite (FeO) is a promising visible-light-active semiconductor material for photoelectrocatalytic applications; however, it has yet to achieve its theoretical maximum efficiency. Researchers globally are making significant efforts to enhance its performance and surpass the current efficiency limitations. Here, we report the photoelectrocatalytic performance of Ti Fe O films deposited by atomic layer deposition (ALD) using FeCp and Ti(OMe) as precursors. The response surface methodology (RSM) with a face-centered central composite design (FC-CCD) was used to model and optimize the photocurrent response of Ti Fe O thin film photoanodes. Deposition parameters, including the cycle ratio of TiO to FeO, total number of ALD cycles, and deposition temperature, were selected as independent variables, while the photocurrent density (PCD) at 1.23 and 1.70 V vs RHE was used as the response variable. Thin film depositions were carried out according to the FC-CCD design matrix, followed by postannealing at 500 °C for 1 h in air. The films were then evaluated for their photocurrent response using a photoelectrochemical cell under standard AM 1.5G illumination, 100 mW/cm. The experimental photocurrent responses were fitted to a second-order polynomial equation, resulting in the development of a mathematical model that establishes a relationship between the deposition parameters and PCD of Ti Fe O photoanode. Analysis of model parameters revealed that film thickness and dopant concentration are the most significant factors influencing the PCD of Ti Fe O photoanode. This study confirms that RSM-based FC-CCD can be efficiently applied for the modeling and optimization of photocurrent response of Ti Fe O photoanodes.
赤铁矿（FeO）是一种用于光电催化应用的很有前景的可见光活性半导体材料；然而，它尚未达到其理论最大效率。全球的研究人员都在做出巨大努力来提高其性能并突破当前的效率限制。在此，我们报告了使用二茂铁（FeCp）和四甲基钛（Ti(OMe)）作为前驱体通过原子层沉积（ALD）制备的Ti Fe O薄膜的光电催化性能。采用具有面心中心复合设计（FC - CCD）的响应面方法（RSM）对Ti Fe O薄膜光阳极的光电流响应进行建模和优化。选择包括TiO与FeO的循环比、ALD循环总数和沉积温度在内的沉积参数作为自变量，而相对于可逆氢电极（RHE）在1.23 V和1.70 V时的光电流密度（PCD）用作响应变量。根据FC - CCD设计矩阵进行薄膜沉积，然后在空气中500 °C退火1 h。然后在标准AM 1.5G光照（100 mW/cm）下使用光电化学池评估薄膜的光电流响应。将实验光电流响应拟合到二阶多项式方程，从而建立了一个数学模型，该模型确定了Ti Fe O光阳极的沉积参数与PCD之间的关系。对模型参数的分析表明，膜厚度和掺杂剂浓度是影响Ti Fe O光阳极PCD的最显著因素。本研究证实基于RSM的FC - CCD可有效地应用于Ti Fe O光阳极光电流响应的建模和优化。
