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Academic Dry Goods | Application of Titanium Dioxi (10th Jan 23 at 2:19am UTC)
Original Title: Academic Dry Goods | Application of Titanium Dioxide in Perovskite Solar Cells Click "Material Person" above to subscribe to us Click "Material Person" above to subscribe to us I. Introduction In recent years, perovskite solar cells have rapidly become a global research hotspot in the field of solar cells because of their significant advantages such as low manufacturing cost and high efficiency. The theoretical photoelectric conversion efficiency of perovskite solar cells can reach 26%, which is close to the level of monocrystalline silicon solar cells (25.6%). The photoelectric conversion efficiency of the latest reported perovskite solar cells reaches 20.1% [1], which is much higher than that of polycrystalline silicon solar cells (18%), and has a very broad market application prospect. In perovskite solar cells, nano-TiO2 has been widely used as electron collection and transport materials due to its appropriate band gap, good Photoelectrochemical stability and simple fabrication process, and is usually used to fabricate dense layers (hole blocking layers) and porous layers (electron transport layers) [2]. As one of the important components of solar cells, the crystal size, particle size and preparation method of TiO2 will significantly affect the photovoltaic performance of solar cells. Fig. 1 Schematic diagram of the working principle of perovskite solar cells [3]: (A) a perovskite solar cell with a porous TiO2 layer; (B) Planar structured perovskite solar cell without porous layer. II. TiO2 dense layer Carrier recombination can seriously affect the photoelectric performance of solar cells and significantly reduce the photoelectric conversion efficiency. In solid-state solar cells, the hole transport layer (HTM) forms an ohmic contact with the transparent conductive electrode (FTO), which leads to the recombination of carriers (hole-electron) and seriously reduces the photoelectric conversion efficiency of the cell. The dense layer between the FTO and the porous layer can effectively avoid the direct contact between the substrate and the HTM, and inhibit the migration of electrons from the FTO to the HTM. The interface recombination is related to the carrier concentration on both sides of the interface. If there is no dense layer, the direct contact between perovskite and FTO will inevitably lead to serious electron-hole recombination; Due to the existence of the dense layer, the carrier concentration at one side of both the FTO/TiO2 and TiO2/perovskite interfaces is low, and the dense layer can prevent the reverse migration of holes, so that the electron recombination can be greatly reduced, and the device performance is improved. The existence of the dense layer helps to improve the electron collection efficiency, thereby improving the photoelectric performance of the cell. The dense layer with excellent performance needs to meet the following three requirements [4]: (1) good optical performance, so as not to affect the absorption of visible light by the perovskite layer; (2) the energy band structure is matched with the electrodes, sensitizing materials, etc., and the purpose of efficiently and selectively injecting the required carriers and blocking another carrier is achieved through the appropriate energy band structure between the functional layers of the cell; (3) that thickness of the dense lay film is appropriate. TiO2 is the most commonly used dense layer material, but its electron mobility is low, so n-type metal oxide semiconductors with good optical properties, high carrier mobility and band matching, such as SnO2 and ZnO, are also used to make dense layers of perovskite solar cells. Expand the full text Fig. 2 Schematic diagram of a typical perovskite solar cell structure [5]. (A) Meso-structured perovskite solar cells; (B) Planar heterostructure perovskite solar cells. 2.1 Preparation method of dense layer TiO2 exists in nature in three forms: rutile, anatase, and brookite. The rutile phase is the most stable of the three. When the temperature is higher than 650 ° C, the anatase phase will begin to transform into the rutile phase, while brookite is only an intermediate phase in the crystallization process of anatase, and generally only exists stably in minerals with impurities. TiO2 anatase phase crystals are the most used in perovskite solar cell research.
Table 1 Performance comparison of typical perovskite solar cells with TiO2 as the electron transport layer [6] The preparation methods of dense layer mainly include spin coating, spray pyrolysis, atomic layer deposition, microwave sintering, magnetron sputtering, etc. Generally, spin coating and spray pyrolysis are simple and easy to operate. Dense layers of other metal oxides can be prepared in essentially the same way. However, both spin-coating and spray pyrolysis require high temperature annealing at 500 ° C to transform anatase TiO2 into anatase phase and improve its ability to transport electrons, which limits the application of anatase TiO2 on flexible substrates. Moreover, the thermal contraction during the phase transformation process will leave holes on the surface of the film, making the connectivity between particles worse [2]. Therefore, the preparation of dense anatase TiO2 at low temperature has become one of the important research directions of perovskite solar cells. The reported low-temperature fabrication methods of TiO2 dense layers include atomic layer deposition (ALD, 200 ° C), spin-coating of anatase TiO2 particles (< 150 ° C), low temperature plasma enhanced atomic layer deposition (PEALD, 80 ° C) and low temperature chemical bath deposition (70 ℃). 2.2 Interface optimization of the dense layer On the basis of perovskite thin film materials with regular morphology, the device performance mainly depends on the reasonable design of device structure and the matching of interface energy levels. In addition, the behavior of carrier migration and recombination at the interface between layers is not only related to the aggregation morphology of the active layer, but also depends on the size of the interface barrier between the electron transport layer or the hole transport layer and the electrode. In order to obtain more efficient and stable solar cells, the contact interface is usually optimized, such as passivation of the surface of titanium dioxide. The photoelectric conversion efficiency of the solar cell can be improved by depositing a thin layer of Sb2S3, Cs2CO3 (2 nm) and other materials on the TiO2 dense layer as a common dense layer. The TiO2 dense layer was modified by C60-SAM, TiCl4 and UV (O3) treatment, which can improve the contact between the dense layer and the perovskite layer, promote charge transport and reduce electron recombination, and improve the conversion efficiency. The graphene nanosheet/nano titanium dioxide composite material is used as an electron transmission layer, and the characteristics of high conductivity, proper work function (between FTO and TiO2) and the like of graphene are utilized to provide a high-speed channel for electron transmission and collection, so that the electron transmission performance of the material is improved, the series resistance of the battery is obviously reduced, And the short-circuit current and the fill factor are obviously improved. There is a Schottky barrier at the interface between transparent conductive oxide (ITO or FTO) and electron transport layer TiO2, which will destroy the performance of the device when the barrier is too large. The electron collection efficiency can be improved by adjusting the work function of the metal to be close to the Fermi level of TiO2. The Y-doped compact TiO2 material is used as an electron transport layer, and the surface of the ITO conductive glass is modified, so that the interface potential barrier between the electron transport layer/transparent conductive oxide can be reduced, the electron transport is facilitated, and the photoelectric conversion efficiency of the solar cell is improved. In addition, Al doping, Zr doping and Nb doping can improve the performance of TiO2 dense layer. 2.3 Thickness of dense layer Increasing the thickness of the dense layer can improve the coverage, reduce the number of holes in the dense layer, and reduce the recombination rate. At the same time, the resistance of the dense layer itself will also affect the performance of the battery. The dense layer resistance of the material was determined to be related to the dense layer thickness. The increase of thickness will lead to the increase of dense layer resistance, affect the series resistance of the whole cell and reduce the efficiency of the cell. Therefore, an efficient dense layer usually needs to reduce the thickness as much as possible on the premise of meeting the high coverage. If there is no dense layer or the thickness of the dense layer is too thin, the FTO can not be completely covered by titanium dioxide, resulting in direct contact between the perovskite film and FTO, which leads to the increase of electron-hole recombination rate on the surface of FTO and serious current leakage. A dense layer that is too thin also affects the coverage of the perovskite sensitizing layer; if the dense layer is too thick, electrons are recombined before being transported from the perovskite layer to the conductive substrate. At present, titanium filler rod , the optimized thickness of the dense layer is generally 30 to 100 nm.
III. TiO2 porous layer At present, most PSCs utilize submicron-thick porous metal oxide films to adsorb perovskite, which are called porous layers. Similar to the dense layer materials, semiconductors with matching energy level structure and high carrier mobility can be used as electron (or hole) transport layer materials with mesoscopic structure. The electron transport layer represented by TiO2 mesoporous nanoparticles has been widely used in perovskite batteries. Because perovskite materials also have good electron transport properties, high band gap oxides such as Al2O3 and ZrO2 can also be used to make porous layers of perovskite solar cells. Mesoporous TiO2 has a large specific surface area, which is convenient for the maximum adsorption of perovskite materials and provides a space for the oriented growth of perovskite films. In addition, the mesoporous TiO2 can be fully contacted with the perovskite material to ensure maximum photogenerated charge separation and charge injection. 3.1 Particle Size, Pore Size, and Film Thickness The thickness of the porous layer has a crucial effect on the perovskite film, and its presence contributes to the complete conversion of PbI2 to perovskite. It is reported that the size of TiO2 particles not only affects the implantation of precursors and the contact between perovskite crystals and TiO2, but also affects the charge transport kinetics at the perovskite/TiO2 interface. With the increase of the thickness of the porous layer, the dark current in the TiO2 porous material will also increase linearly, resulting in the decrease of electron concentration and voltage. When the perovskite completely fills the pores of TiO2, the direct contact between TiO2 and the hole transport layer can be effectively avoided, and the electron recombination is reduced. The large pore size in porous TiO2 is also more conducive to the filling of perovskite particles. In fact, TiO2 particle size, pore size and film thickness do not have a linear relationship with the photoelectric performance of the cell, and these parameters are mutually influenced and interacted. This factor is also one of the reasons for the unstable efficiency of perovskite solar cells, and only by exploring their optimal conditions can the whole photovoltaic device be further optimized. 3.2 Crystal form and morphology Due to the better electron transport properties of anatase phase titanium dioxide, it is often used as electron transport material in photovoltaic devices, and a few researchers use rutile phase titanium dioxide. In addition to the crystal form of titanium dioxide, the morphology has an important impact on the light absorption, electron transport and electron capture of the cell. Titanium dioxide nanosheets can improve the contact between perovskite and porous layer, and titanium dioxide nanotubes with less grain boundaries can significantly improve the light absorption and electron collection efficiency. The porous nano-TiO2 fibers with different diameters and lengths were prepared by electrospinning. The results showed that the fibers with too small diameter were discontinuously distributed, and the fibers with too large diameter were arranged too closely, which hindered the adsorption of perovskite. Fig. 3 Structure diagram of different nanorod lengths [2] 3.3 Modification of porous TiO2 Surface treatment and doping are effective means to modify titanium dioxide materials, and the properties of materials can be significantly improved by reasonable control of conditions. The Nb-doped rutile-type titanium dioxide nanorods are used as photoanodes, so that the photoelectric conversion efficiency of the solar cell is remarkably improved; MgO is used as a compact layer, and the porous TiO2 with a small part of MgO adsorbed is used as a skeleton layer, so that the effective injection of electrons is facilitated, and the recombination of carriers is reduced. The interfacial contact between TiO _ 2 and CH _ 3NH _ 3PbX _ 3 plays an important role in determining the growth of perovskite crystal and the charge separation. Although TiO2 has a suitable energy level and generally acts as an electron transport layer to block holes, it has poor conductivity, which results in additional ohmic losses and an undesirable space charge distribution. The Y-doped titanium dioxide is used as a porous layer, which can not only improve the morphology of the perovskite layer, but also enhance the adsorption of the perovskite layer and the electron transport performance in the battery. Al2O3, ZnO and ZnSO4 are less used in perovskite solar cells because their comprehensive properties are far inferior to those of TiO2.
3.4 Stability In terms of stability, the device performance of perovskite solar cells based on mesoporous TiO2 structure decays rapidly under UV irradiation due to the desorption of oxygen on the surface of TiO2 itself. There are many oxygen vacancies or defects on the surface of TiO2, and these deep level defects will adsorb oxygen radicals in the air, and this adsorption is unstable. TiO2 generates electron-hole pairs under the excitation of ultraviolet light. The holes in the valence band react with oxygen radicals and release oxygen molecules, thus forming a free electron and a positively charged oxygen vacancy in the conduction band. The free electron quickly recombines with the holes in HTM. However, the energy level of the defect state caused by the oxygen vacancy is relatively deep, and when the photogenerated electrons are transferred to it, it is difficult to jump to the conduction band again, so they can only recombine with the internal holes, resulting in a decrease in short-circuit current and a decline in cell performance. IV. Outlook Currently, TiO2 is the most widely used electron transport layer material in perovskite solar cells. In order to further improve the photoelectric conversion efficiency of solar cells, the preparation of nano-TiO2 with high specific surface area, low defects and appropriate pore size is helpful to adsorb more photosensitizers, thus producing greater photocurrent and reducing defects. Doping and surface modification of TiO2 are helpful to improve its performance. References [1] Tan, H., et al., Efficient and stable solution-processed planar perovskite solar cells via contact passivation. Science, 2017. [2] Que Yaping, Weng Jian, Hu Linhua et al. Application of TiO 2 in Perovskite Solar Cell [J]. Progress in chemistry , 2016, 28(1): 40-50. [3] Jung H S, Park N G. Perovskite solar cells: from materials to devices[J]. small, 2015, 11(1): 10-25. [4] Wang Weiqi, Zheng Huifeng, Lu Guanhong, et al. Research Progress of Nanometer Metal Oxides in Perovskite Battery [J]. Journal of Inorganic Materials , 2016, 31(9):897-907. [5] Bai Yubing, Wang Qiuying, Lv Ruitao, et al. Progress in Perovskite Solar Cell [J]. Science Bulletin , 2016, 61: 489-500. [6] Yang Ying, Gao Jing, Cui Jiarui, et al. Progress in Perovskite Solar Cell [J]. Journal of Inorganic Materials , 2015, 30(11): 1131-1138. Material People's Network focuses on tracking the progress of science and technology and industry in the field of materials. It brings together master and doctoral students from major universities, front-line scientific researchers and industry practitioners. If you are interested in tracking the progress of science and technology in the field of materials, interpreting high-level articles or commenting on the industry, click "Read the original" below to enter Material People's Network and sign up to join the editorial department. The material person net to each big team invites the manuscript sincerely, the research group newest achievement, the direction summary, the team interview, the experimental skill and so on may contribute,Titanium welding pipe, once the outstanding manuscript is hired, we will offer the remuneration, please contact: Email or QQ: 97482208.
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