The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open...The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.展开更多
The beneficial effect of the alkali metals such as Na and K on the Cu（In.Ga）Se2 （CIGS） and Cu2ZnSn（S,Se）4 （CZTSSe） solar cells has been extensively investigated in the past two decades, however, in most of the...The beneficial effect of the alkali metals such as Na and K on the Cu（In.Ga）Se2 （CIGS） and Cu2ZnSn（S,Se）4 （CZTSSe） solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum （VBM） level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.展开更多
Cu2ZnSn（S,Se）4 （CZTSSe） is considered as the promising absorbing layer materials for solar cells due to its earth-abundant constituents and excellent semiconductor properties. Through solution-processing, such as ...Cu2ZnSn（S,Se）4 （CZTSSe） is considered as the promising absorbing layer materials for solar cells due to its earth-abundant constituents and excellent semiconductor properties. Through solution-processing, such as various printing methods, the fabrication of high perfor- mance CZTSSe solar cell could be applied to mass production with extremely low manufacturing cost and high yield speed. To better fulfill this goal, environmentalfriendly inks/solutions are optimum for further reducing the capital investment on instrument, personnel and environmental safety. In this review, we summarized the recent development of CZTSSe thin films solar cells fabricated with benign solvents, such as water and ethanol. The disperse system can be classified to the true solution （consisting of molecules） and the colloidal suspension （consisting ofnanoparticles）.Three strategies for stabilization （i.e., physical method, chemical capping and self- stabilization） are proposed to prepare homogeneous and stable colloidal nanoinks. The one-pot self-stabilization method stands as an optimum route for preparing benign inks for its low impurity involvement and simple procedure. As-prepared CZTSSe inks would be deposited onto substrates to form thin films through spin-coating, spraying, electrodeposition or successive ionic layer adsorption and reaction （SILAR） method, followed by annealing in a chalcogen （S- or Se-containing） atmosphere to fabricate absorber. The efficiency of CZTSSe solar cell fabricated with benign solvents can also be enhanced by constituent adjustments, doping, surface treatments and blocking layers modifications, etc., and the deeper research will promise it a comparable performance to the non- benign CZTSSe systems.展开更多
Cu2BaSn(S,Se)4薄膜是在Cu2ZnSn(S,Se)4的基础上发展提出的一类新型半导体材料.具有与Cu2ZnSn(S,Se)4相类似的性质特点,如直接带隙、带隙可调(1.5~2.1 e V)、p型半导体特性、大吸光系数、高载流子迁移率和良好化学稳定性等.更重要的是,C...Cu2BaSn(S,Se)4薄膜是在Cu2ZnSn(S,Se)4的基础上发展提出的一类新型半导体材料.具有与Cu2ZnSn(S,Se)4相类似的性质特点,如直接带隙、带隙可调(1.5~2.1 e V)、p型半导体特性、大吸光系数、高载流子迁移率和良好化学稳定性等.更重要的是,Cu2ZnSn(S,Se)4中Cu和Zn原子半径相似,易出现铜锌位置互换形成反位缺陷.而Cu2BaSn(S,Se)4中Ba和Cu的原子半径相差较大,反位缺陷形成能较高,不易形成缺陷.因此通过将Ba取代Zn后形成的Cu2BaSn(S,Se)4能缓解反位缺陷和带边拖尾等问题,使得Cu2BaSn(S,Se)4成为了替代Cu2ZnSn(S,Se)4的可选材料之一.另外Cu2BaSn(S,Se)4具有优异的光电特性,使其成为光电领域非常重要的材料之一.本文主要阐述了近几年来Cu2BaSn(S,Se)4薄膜的研究进展.包括基本特性,如结构和吸光特性等、各种生长方法的优缺点和在太阳能电池及光电化学等领域的研究进展情况.最后总结并展望了Cu2BaSn(S,Se)4的应用前景,为未来的研究提供方向.展开更多
基金Project supported by the Joint Talent Cultivation Funds of NSFC-HN(Grant No.U1604138)the National Natural Science Foundation of China(Grant Nos.21603058 and 51702085)+2 种基金the Innovation Research Team of Science and Technology in Henan Province,China(Grant No.17IRTSTHN028)the Science and Technology Innovation Talents in Universities of Henan Province,China(Grant No.18HASTIT016)the Young Key Teacher Foundation of Universities of Henan Province,China(Grant No.2015GGJS-022)
文摘The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.
基金supported by the National Natural Science Foundation of China(NSFC)under grant nos.61574059 and 61722402the National Key Research and Development Program of China(2016YFB0700700)+1 种基金Shu-Guang program(15SG20)CC of ECNU
文摘The beneficial effect of the alkali metals such as Na and K on the Cu（In.Ga）Se2 （CIGS） and Cu2ZnSn（S,Se）4 （CZTSSe） solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum （VBM） level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.
文摘Cu2ZnSn（S,Se）4 （CZTSSe） is considered as the promising absorbing layer materials for solar cells due to its earth-abundant constituents and excellent semiconductor properties. Through solution-processing, such as various printing methods, the fabrication of high perfor- mance CZTSSe solar cell could be applied to mass production with extremely low manufacturing cost and high yield speed. To better fulfill this goal, environmentalfriendly inks/solutions are optimum for further reducing the capital investment on instrument, personnel and environmental safety. In this review, we summarized the recent development of CZTSSe thin films solar cells fabricated with benign solvents, such as water and ethanol. The disperse system can be classified to the true solution （consisting of molecules） and the colloidal suspension （consisting ofnanoparticles）.Three strategies for stabilization （i.e., physical method, chemical capping and self- stabilization） are proposed to prepare homogeneous and stable colloidal nanoinks. The one-pot self-stabilization method stands as an optimum route for preparing benign inks for its low impurity involvement and simple procedure. As-prepared CZTSSe inks would be deposited onto substrates to form thin films through spin-coating, spraying, electrodeposition or successive ionic layer adsorption and reaction （SILAR） method, followed by annealing in a chalcogen （S- or Se-containing） atmosphere to fabricate absorber. The efficiency of CZTSSe solar cell fabricated with benign solvents can also be enhanced by constituent adjustments, doping, surface treatments and blocking layers modifications, etc., and the deeper research will promise it a comparable performance to the non- benign CZTSSe systems.
文摘Cu2BaSn(S,Se)4薄膜是在Cu2ZnSn(S,Se)4的基础上发展提出的一类新型半导体材料.具有与Cu2ZnSn(S,Se)4相类似的性质特点,如直接带隙、带隙可调(1.5~2.1 e V)、p型半导体特性、大吸光系数、高载流子迁移率和良好化学稳定性等.更重要的是,Cu2ZnSn(S,Se)4中Cu和Zn原子半径相似,易出现铜锌位置互换形成反位缺陷.而Cu2BaSn(S,Se)4中Ba和Cu的原子半径相差较大,反位缺陷形成能较高,不易形成缺陷.因此通过将Ba取代Zn后形成的Cu2BaSn(S,Se)4能缓解反位缺陷和带边拖尾等问题,使得Cu2BaSn(S,Se)4成为了替代Cu2ZnSn(S,Se)4的可选材料之一.另外Cu2BaSn(S,Se)4具有优异的光电特性,使其成为光电领域非常重要的材料之一.本文主要阐述了近几年来Cu2BaSn(S,Se)4薄膜的研究进展.包括基本特性,如结构和吸光特性等、各种生长方法的优缺点和在太阳能电池及光电化学等领域的研究进展情况.最后总结并展望了Cu2BaSn(S,Se)4的应用前景,为未来的研究提供方向.
