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A Review of Perovskite Photovoltaic Materials' Synthesis And materials Review A Review of Perovskite Photovoltaic Materials’ Synthesis and Applications via Chemical Vapor Deposition Method Xia Liu 1,2,3, Lianzhen Cao 1,2,3,*, Zhen Guo 2,4,5,*, Yingde Li 1, Weibo Gao 3,* and Lianqun Zhou 2,* 1 Department of Physics and Optoelectronic Engineering, Weifang University, Weifang 261061, Shandong, China; [email protected] (X.L.); [email protected] (Y.L.) 2 Chinese Academy of Sciences Key Lab of Bio-Medical Diagnostics, Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou 215163, Jiangsu, China 3 Division of Physics and Applied Physics School of Physical and Mathematical Sciences Nanyang Technological University, Singapore 637371, Singapore 4 Shandong Guo Ke Medical Technology Development Co., Ltd., Jinan 250001, Shandong, China 5 Zhongke Mass Spectrometry (Tianjin) Medical Technology Co., Ltd., Tianjin 300399, China * Correspondence: [email protected] (L.C.); [email protected] (Z.G.); [email protected] (W.G.); [email protected] (L.Z.) Received: 31 August 2019; Accepted: 8 October 2019; Published: 11 October 2019 Abstract: Perovskite photovoltaic materials (PPMs) have emerged as one of superstar object for applications in photovoltaics due to their excellent properties—such as band-gap tunability, high carrier mobility, high optical gain, astrong nonlinear response—as well as simplicity of their integration with other types of optical and electronic structures. Meanwhile, PPMS and their constructed devices still present many challenges, such as stability, repeatability, and large area fabrication methods and so on. The key issue is: how can PPMs be prepared using an effective way which most of the readers care about. Chemical vapor deposition (CVD) technology with high efficiency, controllability, and repeatability has been regarded as a cost-effective road for fabricating high quality perovskites. This paper provides an overview of the recent progress in the synthesis and application of various PPMs via the CVD method. We mainly summarize the influence of different CVD technologies and important experimental parameters (temperature, pressure, growth environment, etc.) on the stabilization, structural design, and performance optimization of PPMS and devices. Furthermore, current challenges in the synthesis and application of PPMS using the CVD method are highlighted with suggested areas for future research. Keywords: atmospheric pressure CVD; low pressure CVD; hybrid CVD; aerosol assisted CVD; pulsed CVD; perovskite photovoltaic nanomaterials; stabilization; structural design; performance optimization; solar cells 1. Introduction Perovskite is a kind of material with the same crystal structure as calcium titanate (CaTiO3), which was discovered by Gustav Rose in 1839 [1]. The perovskite material (PM) structure formula is generally ABX3, where A and B are two cations and X is anion, as shown in Figure1[2]. This unique crystal structure gives it many unique physical and chemical properties, such as broadband bandgap tunability, high carrier mobility, high optical gain, strong nonlinear response, and simplicity of their integration with other types of optical and electronic structures [3–8]. Due to its excellent physical and Materials 2019, 12, 3304; doi:10.3390/ma12203304 www.mdpi.com/journal/materials Materials 2019, 12, 3304 2 of 17 chemicalMaterials 2019 properties,, 12, x FOR PEER especially REVIEW optical properties, perovskite materials are now widely applied2 of 16 for constructing photovoltaic solar cells (PSCs) [2,9–11]. Figure 1. Crystal structure of the perovskite ABX3 form. Figure 1. Crystal structure of the perovskite ABX3 form. Up to now, great progress has been made in the preparation and application of bulk PPMs. The perovskiteUp to now, familygreat progress now includes has been hundreds made in the of preparation substances, and ranging application from of organic bulk PPMs materials,. The inorganicperovskite materials family now to organic–inorganic includes hundreds materials, of substances, from polycrystalline ranging from organic film to bulk materials, single inorganic crystal [12 ]. However,materials introductionto organic–inorganic of manydefects materials, and grainfrom boundariespolycrystalline in three-dimensional film to bulk single (3D) crystal bulk PPMS [12]. is unavoidableHowever, introduction [13], which of inevitably many defects degrade and itsgrain optoelectronic boundaries in properties. three-dimensional Recently, (3D) low-dimensional bulk PPMS PPMSis unavoidable with high [ quality13], which have inevitably begun to receivedegrade increasingits optoelectronic attention, properties. primarily forRecently, their tunablelow- opticaldimensional and electronic PPMS with properties high quality due tohave quantum-size begun to receive effects increasing as well as attention, their enhanced primarily photoelectric for their tunable optical and electronic properties due to quantum-size effects as well as their enhanced performance compared with bulk materials. Moreover, perovskites are considered to be a class of photoelectric performance compared with bulk materials. Moreover, perovskites are considered to important low-dimensional layered materials, whose optical properties can be controlled by varying the be a class of important low-dimensional layered materials, whose optical properties can be controlled number of layers, particularly at thicknesses lower than their exciton Bohr radius. Therefore, the shape-, by varying the number of layers, particularly at thicknesses lower than their exciton Bohr radius. size-, and thickness-controlled synthesis of low-dimensional PPMs has recently been a hot topic of Therefore, the shape-, size-, and thickness-controlled synthesis of low-dimensional PPMs has recently research. Various low-dimensional morphologies, including zero-dimensional (0D) morphologies, been a hot topic of research. Various low-dimensional morphologies, including zero-dimensional (0D) such as quantum dots and nanoparticles; one-dimensional (1D) morphologies, such as nanowires and morphologies, such as quantum dots and nanoparticles; one-dimensional (1D) morphologies, such nanorods; and two-dimensional (2D) morphologies, such as nanoplates and nanosheets, have been as nanowires and nanorods; and two-dimensional (2D) morphologies, such as nanoplates and preparednanosheets, and have applied been [ 14prepared–21]. and applied [14–21]. DueDue to to potentialpotential applicationsapplications of perovskite material materialss (PM (PMs)s) in in photovoltaics photovoltaics wide wide spread spread interest interest hashas focused focused onon exploringexploring variousvarious synthesis methods methods to to obtain obtain high high quality quality perovskite perovskite materials materials for for constructingconstructing designed designed devices devices with with improved improved performance. performance. Up Up to to now, now, many many synthesis synthesis methods—such methods— assuch solution as solution process process [4,22– [4,2622], thermal–26], thermal evaporation evaporation process process [27], [ flash27], flash evaporation evaporation [28], [28 doctor-blade], doctor- coatingblade coating method method [29], slot-die [29], coatingslot-die methodcoating [30method], spray [30 deposition], spray deposition [31], ink-jet [3 printing1], ink-jet method printing [32 ], vapor-assistedmethod [32], vapor solution-assisted process solution (VASP) process [33], and (VASP) so on—have [33], and been so on developed—have been for preparingdeveloped PPMsfor withpreparing well-designed PPMs with dimensions well-designed for exploring dimensions factors for exploring which plays factors key which role inplays dominating key role theirin properties.dominating Among their properties. various approaches, Among various the mostapproaches, studied the solution most studied method solution not only method achieves not highlyonly eachievesfficient perovskite highly efficient solar perovskite cells (PSCs) solar but cells also (PSCs has a) but cost also advantage. has a cost However, advantage. the However, uncontrolled the rapiduncontrolled liquid reaction rapid liquid often generatesreaction often rough, generates porous, rough and less-stable, porous, and perovskite less-stable films perovskite with incomplete films conversions,with incomplete resulting conversions, in large resulting variations in on large film variations morphology on film and morphology Photovoltaic and (PV) Photovoltaic response [ 24(PV–26) ]. Inversely,response thermal[24–26]. evaporationInversely, ther canmal generate evaporation high-quality can generate perovskite high films-quality with smoothperovskite and films pinhole-free with morphologies.smooth and pinhole However,-free there morphologies. are a few of However, disadvantages there in are thermal a few evaporation of disadvantages process, in such thermal as low materialevaporation utilization, process, and such high as equipmentlow material investment utilization, and and energy high equipment consumption, investment hampering and its energy further applicationconsumption, [27 ,hampering28]. The rest its technologiesfurther application often produce[27,28]. The poor rest perovskite technologies film often quality, produce and are poor also diperovskitefficult to scale film up quality, [29–32 ].and VASP are methods also difficult require to manipulations scale up [29 protecting–32]. VASP atmosphere, methods andrequire show poormanipulations controllability protecting and versatility, atmosphere, unsuitable
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