CN217182188U - A perovskite/perovskite/silicon-germanium-based triple junction solar cell - Google Patents

Abstract

The utility model discloses a perovskite/perovskite silicon-germanium base triple junction tandem solar cell relates to solar cell technical field, including back electrode, the battery at the bottom of silicon-germanium, narrow band gap perovskite battery, wide band gap perovskite battery and last electrode that stack gradually, battery series connection sets up at the bottom of wide band gap perovskite top battery, narrow band gap perovskite battery and the silicon-germanium, and wide band gap perovskite battery is connected through first tunneling junction with narrow band gap perovskite battery, and the battery passes through the second tunneling junction at the bottom of narrow band gap perovskite battery and the silicon-germanium and is connected. Meanwhile, the perovskite solar cell is low in cost, and the silicon-germanium bottom cell also has the characteristics of strong intrinsic stability and low price, so that the perovskite/silicon-germanium triple-junction laminated solar cell is a novel photovoltaic device with high theoretical efficiency, low cost and high practical value.

Description

Translated fromChinese

一种钙钛矿/钙钛矿/硅-锗基三结叠层太阳能电池A perovskite/perovskite/silicon-germanium-based triple junction solar cell

技术领域technical field

本实用新型涉及太阳能电池技术领域，尤其涉及一种钙钛矿/钙钛矿/硅-锗基三结叠层太阳能电池。The utility model relates to the technical field of solar cells, in particular to a perovskite/perovskite/silicon-germanium-based triple junction stacked solar cell.

背景技术Background technique

自1954年第一块太阳能电池问世以来，光伏技术不断得到突破。经过了近些年的快速发展，第三代太阳能电池中的钙钛矿太阳能电池因其易制备、低成本、带隙可调等众多优点在国际上受到广泛关注，成为光电和材料领域的新星。但是由于太阳辐射光谱的范围非常宽，仅仅依靠单节的钙钛矿太阳能电池，仅能将太阳辐射中的一小部分转化为电能。为了突破单结太阳能电池的效率极限，迫切需要研发低成本高效率的太阳能电池。Since the advent of the first solar cell in 1954, photovoltaic technology has continued to make breakthroughs. After rapid development in recent years, perovskite solar cells in the third-generation solar cells have attracted wide attention internationally due to their easy preparation, low cost, adjustable band gap and many other advantages, and have become a new star in the field of optoelectronics and materials. . However, due to the very wide range of the solar radiation spectrum, only a single-cell perovskite solar cell can convert only a small part of the solar radiation into electricity. In order to break through the efficiency limit of single-junction solar cells, there is an urgent need to develop low-cost and high-efficiency solar cells.

将不同带隙宽度的电池按照带隙从大到小的顺序叠加起来，可以大幅度拓宽电池的吸收光谱范围，提升太阳能转化效率。同时，钙钛矿太阳能电池有着带隙可调、制作简单的优点，非常适合制备高性能的叠层太阳能电池。By stacking cells with different band gap widths in the order from large to small, the absorption spectrum range of the cell can be greatly broadened and the solar energy conversion efficiency can be improved. At the same time, perovskite solar cells have the advantages of adjustable band gap and simple fabrication, which are very suitable for the fabrication of high-performance tandem solar cells.

实用新型内容Utility model content

本申请实施例通过提供一种钙钛矿/钙钛矿/硅-锗基三结叠层太阳能电池，在保证低成本的情况下，提升太阳能电池的转化效率。The embodiments of the present application provide a perovskite/perovskite/silicon-germanium-based triple junction tandem solar cell, so as to improve the conversion efficiency of the solar cell while ensuring low cost.

一种钙钛矿/钙钛矿/硅-锗基三结叠层太阳能电池，包括依次层叠的背电极、硅-锗底电池、窄带隙钙钛矿电池、宽带隙钙钛矿电池和上电极，所述宽带隙钙钛矿顶电池、所述窄带隙钙钛矿电池和所述硅-锗底电池串联设置，所述宽带隙钙钛矿电池与所述窄带隙钙钛矿电池通过第一隧穿结连接，所述窄带隙钙钛矿电池与所述硅-锗底电池通过第二隧穿结连接。A perovskite/perovskite/silicon-germanium-based triple-junction tandem solar cell, comprising a back electrode, a silicon-germanium bottom cell, a narrow-bandgap perovskite cell, a wide-bandgap perovskite cell, and an upper electrode stacked in sequence , the wide-bandgap perovskite top cell, the narrow-bandgap perovskite cell and the silicon-germanium bottom cell are arranged in series, and the wide-bandgap perovskite cell and the narrow-bandgap perovskite cell pass through the first A tunnel junction is connected, and the narrow bandgap perovskite cell is connected with the silicon-germanium bottom cell through a second tunnel junction.

进一步地，所述硅-锗底电池包括依次层叠的第一掺杂层、本征层和第二掺杂层，所述本征层为硅锗合金层，所述本征层的厚度为400～600nm，所述本征层的带隙是0.67～1.12eV。Further, the silicon-germanium bottom cell includes a first doped layer, an intrinsic layer and a second doped layer stacked in sequence, the intrinsic layer is a silicon germanium alloy layer, and the thickness of the intrinsic layer is 400 ~600 nm, the band gap of the intrinsic layer is 0.67-1.12 eV.

进一步地，所述第一掺杂层和第二掺杂层分别为P型层和N型层，或N型层和P型层；所述P型层为掺硼的非晶硅薄膜层，所述N型层材料为掺磷的非晶硅薄膜层，所述第一掺杂层的厚度为30～60nm，所述第二掺杂层的厚度为30～60nm。Further, the first doped layer and the second doped layer are respectively a P-type layer and an N-type layer, or an N-type layer and a P-type layer; the P-type layer is a boron-doped amorphous silicon thin film layer, The material of the N-type layer is a phosphorus-doped amorphous silicon thin film layer, the thickness of the first doped layer is 30-60 nm, and the thickness of the second doped layer is 30-60 nm.

进一步地，所述宽带隙钙钛矿太阳能电池包括依次层叠的上电极、第一载流子传输层、宽带隙钙钛矿光吸收层和第二载流子传输层，所述宽带隙钙钛矿光吸收层的带隙范围为1.7～2.1eV。Further, the wide-bandgap perovskite solar cell comprises an upper electrode, a first carrier transport layer, a wide-bandgap perovskite light absorption layer and a second carrier-transport layer stacked in sequence, the wide-bandgap perovskite The band gap of the mineral light absorption layer ranges from 1.7 to 2.1 eV.

进一步地，所述宽带隙钙钛矿光吸收层为APbX₃结构层，其中A包括Cs⁺、CH₃NH₃⁺、CH(NH₂)₂⁺中的至少一种，但不限于此；X为Cl^-、Br^-、I^-中的至少一种。Further, the wide-bandgap perovskite light absorption layer is an APbX₃ structure layer, wherein A includes at least one of Cs⁺ , CH₃ NH₃⁺ , and CH(NH₂ )₂⁺ , but not limited thereto; X is at least one of Cl^- , Br^- and I^- .

进一步地，所述窄带隙钙钛矿太阳能电池包括依次层叠的第三载流子传输层、窄带隙钙钛矿光吸收层和第四载流子传输层，所述窄带隙钙钛矿光吸收层的带隙范围是1.2～1.8eV。Further, the narrow-bandgap perovskite solar cell includes a third carrier transport layer, a narrow-bandgap perovskite light absorption layer and a fourth carrier transport layer that are stacked in sequence, and the narrow-bandgap perovskite light absorbs The band gap of the layers ranges from 1.2 to 1.8 eV.

进一步地，所述窄带隙钙钛矿光吸收层为ABX₃结构，其中A包括Cs⁺、CH₃NH₃⁺、CH(NH₂)₂⁺中的至少一种，但不限于此；B为Pb²⁺、Sn²⁺中的至少一种；X为Cl^-、Br^-、I^-中的至少一种。Further, the narrow bandgap perovskite light absorbing layer has an ABX₃ structure, wherein A includes at least one of Cs⁺ , CH₃ NH₃⁺ , and CH(NH₂ )₂⁺ , but is not limited to this; B is At least one of Pb²⁺ and Sn²⁺ ; X is at least one of Cl^- , Br^- and I^- .

进一步地，所述第一隧穿结为致密层，所述致密层为N型半导体材料层或P型半导体材料层。Further, the first tunnel junction is a dense layer, and the dense layer is an N-type semiconductor material layer or a P-type semiconductor material layer.

进一步地，所述第二隧穿结为金属氧化物层，所述金属氧化物为氧化锡、氧化钛、氧化锌、氧化铟锡、掺杂氧化锡、掺杂氧化钛、掺铝氧化锌和掺锑氧化锡中的至少一种。Further, the second tunneling junction is a metal oxide layer, and the metal oxide is tin oxide, titanium oxide, zinc oxide, indium tin oxide, doped tin oxide, doped titanium oxide, aluminum doped zinc oxide and At least one of antimony-doped tin oxide.

进一步地，所述第一隧穿结的厚度为20nm至300nm，第二隧穿结的厚度为20nm至300nm。Further, the thickness of the first tunneling junction is 20 nm to 300 nm, and the thickness of the second tunneling junction is 20 nm to 300 nm.

本申请实施例中提供的一个或多个技术方案，至少具有如下技术效果或优点：One or more technical solutions provided in the embodiments of this application have at least the following technical effects or advantages:

本申请的一种钙钛矿/钙钛矿/硅-锗基三结叠层太阳能电池包括依次层叠的背电极、硅-锗底电池、窄带隙钙钛矿电池、宽带隙钙钛矿电池和上电极，所述宽带隙钙钛矿顶电池、所述窄带隙钙钛矿电池和所述硅-锗底电池串联设置，所述宽带隙钙钛矿电池与所述窄带隙钙钛矿电池通过第一隧穿结连接，所述窄带隙钙钛矿电池与所述硅-锗底电池通过第二隧穿结连接。A perovskite/perovskite/silicon-germanium-based triple-junction tandem solar cell of the present application includes a back electrode, a silicon-germanium bottom cell, a narrow-bandgap perovskite cell, a wide-bandgap perovskite cell and upper electrode, the wide band gap perovskite top cell, the narrow band gap perovskite cell and the silicon-germanium bottom cell are arranged in series, the wide band gap perovskite cell and the narrow band gap perovskite cell pass through A first tunneling junction is connected, and the narrow bandgap perovskite cell is connected with the silicon-germanium bottom cell through a second tunneling junction.

宽带隙钙钛矿太阳能电池用于吸收短波波段的太阳光，并使其它波段的太阳光透过，窄带隙钙钛矿太阳能电池用于吸收介于短波和长波之间的波段的太阳光并使长波段太阳光透过，硅-锗底电池用于吸收长波长的太阳光。本申请提供的叠层太阳能电池的带隙接近理论计算的理想值，能够大幅度拓宽太阳光的利用范围，提高太阳能电池的转换效率。锗和硅位于同一主族，锗的带隙为0.67eV，硅的带隙为1.12eV，硅-锗底电池可以通过调节工艺参数来更改带隙宽度，同样具备带隙可调的特点，同时硅-锗底电池还具有本征稳定性强的特性，能够增强钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池的稳定性。Wide-bandgap perovskite solar cells are used to absorb sunlight in the short-wave band and transmit sunlight in other bands, while narrow-band-gap perovskite solar cells are used to absorb sunlight in the band between short and long wavelengths. The long-wavelength sunlight is transmitted through, and the silicon-germanium bottom cell is used to absorb the long-wavelength sunlight. The band gap of the tandem solar cell provided by the present application is close to the theoretically calculated ideal value, which can greatly broaden the utilization range of sunlight and improve the conversion efficiency of the solar cell. Ge and silicon are in the same main group, the band gap of germanium is 0.67eV, and the band gap of silicon is 1.12eV. The silicon-germanium bottom cell can change the width of the band gap by adjusting the process parameters. It also has the characteristics of adjustable band gap. Silicon-germanium bottom cells also have strong intrinsic stability, which can enhance the stability of perovskite/perovskite/silicon-germanium triple junction solar cells.

基于这种理想最佳叠层方案的钙钛矿/钙钛矿/钙钛矿/硅-锗基三节叠层结构的太阳能电池是这样实现49％的理论极限效率的，由于三节叠层为串联关系，因此叠层太阳能电池的电流取决于宽带隙的电池，极限短路电流15.5mA/cm²；叠层太阳能电池的电压由三节叠层相加，宽带隙顶电池电压为2.1V，窄带隙中间电池电压为1.25，硅-锗底电池电压为0.35V，极限开路电压为3.7V；叠层太阳能电池的极限填充因子可以超过0.86。这样能够实现49％的效率。The perovskite/perovskite/perovskite/silicon-germanium-based three-node stacked solar cell based on this ideal optimal stacking scheme achieves a theoretical limit efficiency of 49% in this way. Therefore, the current of the tandem solar cell depends on the wide bandgap cell, and the limit short-circuit current is 15.5mA/cm² ; The cell voltage is 1.25, the silicon-germanium bottom cell voltage is 0.35V, and the limit open circuit voltage is 3.7V; the limit fill factor of the tandem solar cell can exceed 0.86. This enables an efficiency of 49%.

附图说明Description of drawings

为了更清楚地说明本实用新型实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本实用新型的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the drawings in the following description are only some implementations of the present invention. For example, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

图1是本申请实施例中一种钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的示意图；1 is a schematic diagram of a perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in the embodiment of the present application;

图2是本申请实施例中一种钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的各层结构示意图；FIG. 2 is a schematic diagram of each layer structure of a perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in an embodiment of the present application;

图3(a)是本申请实施例中一种正式钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的结构各层结构示意图；3(a) is a schematic diagram of the structure of each layer of a formal perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in the embodiment of the present application;

图3(b)是本申请实施例中一种反式钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的结构各层结构示意图。FIG. 3( b ) is a schematic diagram showing the structure of each layer of a trans-perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in an embodiment of the present application.

附图说明：Description of drawings:

背电极100、Back electrode 100,

硅-锗底电池200、第一掺杂层201、本征层202、第二掺杂层203Silicon-germanium bottom cell 200 , first dopedlayer 201 ,intrinsic layer 202 , second dopedlayer 203

窄带隙钙钛矿电池300、第三载流子传输层301、窄带隙钙钛矿光吸收层302、第四载流子传输层303Narrowbandgap perovskite cell 300 , thirdcarrier transport layer 301 , narrow bandgap perovskitelight absorption layer 302 , fourthcarrier transport layer 303

宽带隙钙钛矿电池400、第一载流子传输层401、宽带隙钙钛矿光吸收层402、第二载流子传输层403、Wide bandgap perovskite battery 400, firstcarrier transport layer 401, wide band gap perovskitelight absorption layer 402, secondcarrier transport layer 403,

上电极500，第一隧穿结600、第二隧穿结700Upper electrode 500,first tunnel junction 600,second tunnel junction 700

具体实施方式Detailed ways

为使本实用新型的目的、技术方案和优点更加清楚，下面将结合附图对本实用新型实施方式作进一步地详细描述。In order to make the objectives, technical solutions and advantages of the present utility model more clear, the embodiments of the present utility model will be further described in detail below with reference to the accompanying drawings.

图1是本申请实施例中一种钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的示意图，如图1所示，本申请的一种钙钛矿/钙钛矿/硅-锗基三结叠层太阳能电池包括依次层叠的背电极、硅-锗底电池、窄带隙钙钛矿电池、宽带隙钙钛矿电池和上电极，所述宽带隙钙钛矿顶电池、所述窄带隙钙钛矿电池和所述硅-锗底电池串联设置，所述宽带隙钙钛矿电池与所述窄带隙钙钛矿电池通过第一隧穿结连接，所述窄带隙钙钛矿电池与所述硅-锗底电池通过第二隧穿结连接。锗和硅位于同一主族，锗的带隙为0.67eV，硅的带隙为1.12eV，硅-锗底电池可以通过调节工艺参数来更改带隙宽度，使得硅-锗底电池具备带隙可调的特点，同时硅-锗电池还具有本征稳定性强的特性；CsPbX₃(X为Cl^-、Br^-和I^-中的至少一种)全无机钙钛矿有着超过2eV的带隙，非常适合作为三结叠层太阳能电池的顶电池。FIG. 1 is a schematic diagram of a perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in an embodiment of the present application. As shown in FIG. 1, a perovskite/calcium The titanium/silicon-germanium-based triple-junction tandem solar cell includes a back electrode, a silicon-germanium bottom cell, a narrow-bandgap perovskite cell, a wide-bandgap perovskite cell, and an upper electrode that are stacked in sequence, the wide-bandgap perovskite The top cell, the narrow-bandgap perovskite cell and the silicon-germanium bottom cell are arranged in series, the wide-bandgap perovskite cell and the narrow-bandgap perovskite cell are connected through a first tunnel junction, and the narrow-bandgap perovskite cell is connected in series. A gap perovskite cell is connected to the silicon-germanium bottom cell through a second tunnel junction. Germanium and silicon are in the same main group, the band gap of germanium is 0.67eV, and the band gap of silicon is 1.12eV. The silicon-germanium bottom cell can change the width of the band gap by adjusting the process parameters, so that the silicon-germanium bottom cell has a band gap that can be adjusted. At the same time, the silicon-germanium battery also has the characteristics of strong intrinsic stability; CsPbX₃ (X is at least one of Cl^- , Br^- and I^- ) all-inorganic perovskite has a band gap of more than 2eV, Very suitable as the top cell of triple junction tandem solar cells.

宽带隙钙钛矿太阳能电池用于吸收短波波段的太阳光，并使其它波段的太阳光透过，窄带隙钙钛矿太阳能电池用于吸收介于短波和长波之间的波段的太阳光并使长波段太阳光透过，硅-锗底电池用于吸收长波长的太阳光。本申请提供的叠层太阳能电池能够大幅度拓宽太阳光的利用范围，提高太阳能电池的转换效率。Wide-bandgap perovskite solar cells are used to absorb sunlight in the short-wave band and transmit sunlight in other bands, while narrow-band-gap perovskite solar cells are used to absorb sunlight in the band between short and long wavelengths. The long-wavelength sunlight is transmitted through, and the silicon-germanium bottom cell is used to absorb the long-wavelength sunlight. The tandem solar cell provided by the present application can greatly expand the utilization range of sunlight and improve the conversion efficiency of the solar cell.

具体地，所述上电极为ITO、IZO、AZO、石墨烯、Ag、Au、Cu金属纳米线中的至少一种。所述背电极为Au、Ag、Ti、Pt、Be中的一种或多种。Specifically, the upper electrode is at least one of ITO, IZO, AZO, graphene, Ag, Au, and Cu metal nanowires. The back electrode is one or more of Au, Ag, Ti, Pt, and Be.

图2是本申请实施例中一种钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的各层结构示意图。如图2所示，所述硅-锗底电池包括依次层叠的第一掺杂层、本征层和第二掺杂层，所述本征层为硅锗合金层，所述本征层的厚度为400～600nm，所述本征层的带隙是0.67～1.12eV。FIG. 2 is a schematic diagram of each layer structure of a perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in an embodiment of the present application. As shown in FIG. 2 , the silicon-germanium bottom cell includes a first doped layer, an intrinsic layer and a second doped layer stacked in sequence, the intrinsic layer is a silicon-germanium alloy layer, and the intrinsic layer is a silicon-germanium alloy layer. The thickness is 400-600 nm, and the band gap of the intrinsic layer is 0.67-1.12 eV.

进一步地，所述宽带隙钙钛矿太阳能电池包括依次层叠的上电极、第一载流子传输层、宽带隙钙钛矿光吸收层和第二载流子传输层。Further, the wide band gap perovskite solar cell includes an upper electrode, a first carrier transport layer, a wide band gap perovskite light absorption layer and a second carrier transport layer stacked in sequence.

进一步地，所述宽带隙钙钛矿光吸收层为APbX₃结构层，其中A包括Cs⁺、CH₃NH₃⁺、CH(NH₂)₂⁺中的至少一种，但不限于此；X为Cl^-、Br^-、I^-中的至少一种。示例性地，宽带隙钙钛矿光吸收层的材料可以为CsPbI_3-xBr_x(其中0<x<3)，所述宽带隙钙钛矿光吸收层的带隙范围为1.7～2.1eV。Further, the wide-bandgap perovskite light absorption layer is an APbX₃ structure layer, wherein A includes at least one of Cs⁺ , CH₃ NH₃⁺ , and CH(NH₂ )₂⁺ , but not limited thereto; X is at least one of Cl^- , Br^- and I^- . Exemplarily, the material of the wide band gap perovskite light absorbing layer can be CsPbI_3-x Br_x (wherein 0<x<3), and the band gap of the wide band gap perovskite light absorbing layer ranges from 1.7 to 2.1 eV .

进一步地，所述窄带隙钙钛矿太阳能电池包括依次层叠的第三载流子传输层、窄带隙钙钛矿光吸收层和第四载流子传输层。Further, the narrow-bandgap perovskite solar cell includes a third carrier transport layer, a narrow-bandgap perovskite light absorption layer and a fourth carrier transport layer stacked in sequence.

进一步地，所述窄带隙钙钛矿光吸收层为ABX₃结构，其中A包括Cs⁺、CH₃NH₃⁺、CH(NH₂)₂⁺中的至少一种，但不限于此；B为Pb、Sn中的至少一种；X为Cl、Br、I中的至少一种，所述窄带隙钙钛矿光吸收层的带隙范围是1.2～1.8eV。Further, the narrow bandgap perovskite light absorbing layer has an ABX₃ structure, wherein A includes at least one of Cs⁺ , CH₃ NH₃⁺ , and CH(NH₂ )₂⁺ , but is not limited to this; B is At least one of Pb and Sn; X is at least one of Cl, Br, and I, and the band gap range of the narrow band gap perovskite light absorption layer is 1.2-1.8 eV.

目前大部分的叠层太阳能电池研究聚焦于全钙钛矿叠层太阳能电池和钙钛矿硅基叠层太阳能电池，这些电池都只有两叠层，两个吸光材料，例如晶硅的带隙维1.12eV，其极限吸收光谱只能到1107nm，钙钛矿具有带隙可调的特点，钙钛矿的最窄带隙也仅仅为1.2eV左右，其极限吸收光谱也在1100nm以下。而太阳光谱范围很宽，这也意味着太阳能电池的转换效率仍然有极大的提升空间。根据Marti和Araujo于1996年发表的太阳能电池理论极限效率表(文章名称：Limiting efficiencies for photovoltaic energyconversion in multigap systems.Solar Energy Materials and Solar Cells.43:203-222)，理论上三叠层太阳能电池的光电转换效率可以达到49.1％，比两叠层的太阳能电池理论光电转换效率42.7％更高，如表1所示。三叠层太阳能电池的最优带隙组合为底电池0.83eV，中间电池1.45eV，顶电池2.26eV。钙钛矿带隙不可能低至0.8eV，得益于硅-锗电池带隙可调的特性(0.67～1.12eV)，所以我们创造性的采用了硅锗材料制备底电池，同时CsPbX₃(X为Cl^-、Br^-和I^-中的至少一种)全无机钙钛矿有着超过2eV的带隙非常适合作为三结叠层太阳能电池的顶电池，结合两者的特性，通过工艺调控，我们实现了三叠层太阳能电池25.04％的转换效率。Most of the current research on tandem solar cells focuses on all-perovskite tandem solar cells and perovskite-silicon-based tandem solar cells, which have only two stacks and two light-absorbing materials, such as the band gap dimension of crystalline silicon. 1.12eV, its limit absorption spectrum can only reach 1107nm, perovskite has the characteristics of adjustable band gap, the narrowest band gap of perovskite is only about 1.2eV, and its limit absorption spectrum is also below 1100nm. The wide range of the solar spectrum means that the conversion efficiency of solar cells still has great room for improvement. According to the theoretical limit efficiency table of solar cells published by Marti and Araujo in 1996 (article title: Limiting efficiencies for photovoltaic energy conversion in multigap systems. Solar Energy Materials and Solar Cells. 43: 203-222), theoretically the three-layer solar cell has a The photoelectric conversion efficiency can reach 49.1%, which is higher than the theoretical photoelectric conversion efficiency 42.7% of the two-layer solar cell, as shown in Table 1. The optimal band gap combination of the tri-tandem solar cell is 0.83 eV for the bottom cell, 1.45 eV for the middle cell, and 2.26 eV for the top cell. The perovskite band gap cannot be as low as 0.8eV. Thanks to the adjustable band gap (0.67-1.12eV) of silicon-germanium batteries, we creatively use silicon-germanium materials to prepare bottom batteries, while CsPbX₃ (X It is at least one of Cl^- , Br^- and I^- ) all-inorganic perovskite with a band gap of more than 2eV is very suitable as the top cell of triple-junction tandem solar cells. Combining the characteristics of the two, through process control, we A conversion efficiency of 25.04% for the tri-tandem solar cell was achieved.

可选地，所述第一载流子传输层材料和第三载流子传输材料选自PTAA、PEDOT：PSS和氧化镍(NiO)其中至少一种，其厚度为5～100nm。Optionally, the first carrier transport layer material and the third carrier transport material are at least one selected from PTAA, PEDOT:PSS and nickel oxide (NiO), and the thickness thereof is 5-100 nm.

可选地，所述第二载流子传输层材料和第四载流子传输材料选自C₆₀、PCBM和SnO₂中的至少一种，其厚度为5～80nm。Optionally, the second carrier transport layer material and the fourth carrier transport material are at least one selected from C₆₀ , PCBM and SnO₂ , and have a thickness of 5-80 nm.

表1 叠层太阳能电池的理论极限效率(Marti和Araujo，1996)Table 1 Theoretical limit efficiency of tandem solar cells (Marti and Araujo, 1996)

进一步地，所述第一隧穿结为致密层，所述致密层为N型半导体材料层或P型半导体材料层。Further, the first tunnel junction is a dense layer, and the dense layer is an N-type semiconductor material layer or a P-type semiconductor material layer.

进一步地，所述第二隧穿结为金属氧化物层，所述金属氧化物为氧化锡、氧化钛、氧化锌、氧化铟锡、掺杂氧化锡、掺杂氧化钛、掺铝氧化锌和掺锌氧化锡中的至少一种。Further, the second tunneling junction is a metal oxide layer, and the metal oxide is tin oxide, titanium oxide, zinc oxide, indium tin oxide, doped tin oxide, doped titanium oxide, aluminum doped zinc oxide and At least one of zinc-doped tin oxide.

进一步地，所述第一隧穿结的厚度为20nm至300nm，第二隧穿结的厚度为20nm至300nm。Further, the thickness of the first tunneling junction is 20 nm to 300 nm, and the thickness of the second tunneling junction is 20 nm to 300 nm.

图3(a)是本申请实施例中一种正式钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的结构各层结构示意图，如图3(a)所示，所述第一载流子传输层为电子传输层时，第二载流子传输层为空穴传输层，所述第三载流子传输层为电子传输层时，第四载流子传输层为空穴传输层，所述第一掺杂层为N型层，第二掺杂层为P型层，所述第二隧穿结与硅-锗底电池的N型层接触。Figure 3(a) is a schematic diagram of the structure of each layer of a formal perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in the embodiment of the present application, as shown in Figure 3(a) , when the first carrier transport layer is an electron transport layer, the second carrier transport layer is a hole transport layer, and when the third carrier transport layer is an electron transport layer, the fourth carrier transport layer The layer is a hole transport layer, the first doped layer is an N-type layer, the second doped layer is a P-type layer, and the second tunnel junction is in contact with the N-type layer of the silicon-germanium bottom cell.

图3(b)是本申请实施例中一种反式钙钛矿/钙钛矿/硅-锗基三结叠层钙钛矿太阳能电池的结构各层结构示意图。如图3(b)所示，所述第一载流子传输层为空穴传输层时，第二载流子传输层为电子传输层，所述第三载流子传输层为空穴传输层，第四载流子传输层为电子传输层，所述第一掺杂层为P型层，第二掺杂层为N型层，所述第二隧穿结与硅-锗底电池的P型层接触。FIG. 3( b ) is a schematic diagram showing the structure of each layer of a trans-perovskite/perovskite/silicon-germanium-based triple junction stacked perovskite solar cell in an embodiment of the present application. As shown in FIG. 3( b ), when the first carrier transport layer is a hole transport layer, the second carrier transport layer is an electron transport layer, and the third carrier transport layer is a hole transport layer The fourth carrier transport layer is an electron transport layer, the first doped layer is a P-type layer, the second doped layer is an N-type layer, and the second tunnel junction is connected to the silicon-germanium bottom cell. P-type layer contacts.

具体地，所述P型层为掺硼的非晶硅层，所述N型层材料为掺磷的非晶硅层，所述第一掺杂层的厚度为30～60nm，所述第二掺杂层的厚度为30～60nm。Specifically, the P-type layer is a boron-doped amorphous silicon layer, the N-type layer material is a phosphorus-doped amorphous silicon layer, the first doped layer has a thickness of 30-60 nm, and the second doped layer has a thickness of 30-60 nm. The thickness of the doped layer is 30-60 nm.

进一步地，所述第一隧穿结为致密层，对于反式结构，其对应的致密层材料包括TiO₂，SnO₂，Zn₂SnO₄中的至少一种，但不限于上述的N型半导体材料；对于正式结构，其对应的致密层材料包括NiO、MoO₃、Cu₂O、CuI中的一种，但不限于上述的P型半导体材料。Further, the first tunnel junction is a dense layer, and for the trans structure, the corresponding dense layer material includes at least one of TiO₂ , SnO₂ , Zn₂ SnO₄ , but is not limited to the above N-type semiconductor Material: For the formal structure, the corresponding dense layer material includes one of NiO, MoO₃ , Cu₂ O, and CuI, but is not limited to the above-mentioned P-type semiconductor material.

示例性地，所述隧穿结可以通过磁控溅射或原子层沉积(ALD)制备，所述底电池可以通过化学气相沉积制备。窄带隙钙钛矿光吸收层和宽带隙钙钛矿光吸收层的制备技术包括旋涂、刮涂、吹气、丝网印刷、喷涂等。Illustratively, the tunnel junction may be fabricated by magnetron sputtering or atomic layer deposition (ALD), and the bottom cell may be fabricated by chemical vapor deposition. The preparation techniques of the narrow-bandgap perovskite light-absorbing layer and the wide-bandgap perovskite light-absorbing layer include spin coating, blade coating, air blowing, screen printing, spray coating, and the like.

下面结合具体实施例来进一步说明本实用新型的钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池的制作方法。The manufacturing method of the perovskite/perovskite/silicon-germanium triple junction tandem solar cell of the present invention will be further described below with reference to specific examples.

实施例1：Example 1:

1.制备硅-锗底电池，包括P型层、本征层、N型层和背电极，具体步骤如下。1. Prepare a silicon-germanium bottom cell, including a P-type layer, an intrinsic layer, an N-type layer and a back electrode, and the specific steps are as follows.

步骤1：对ITO样品玻璃衬底进行清洗，分别使用玻璃水、去离子水、无水乙醇、丙酮超声处理20min。Step 1: The glass substrate of the ITO sample was cleaned, and ultrasonically treated with glass water, deionized water, absolute ethanol and acetone for 20 min respectively.

步骤2：把吹干的样品衬底使用紫外UV处理20min增强浸润性，处理结束后，将处理好的样品放入到培养皿中，然后运送到等离子体气相沉积腔体中进行薄膜制备。Step 2: Treat the dried sample substrate with ultraviolet UV for 20 min to enhance wettability. After the treatment, put the treated sample into a petri dish, and then transport it to a plasma vapor deposition chamber for film preparation.

步骤3：使用PECVD技术制备P型层。把清洗后的ITO玻璃衬底放入真空腔体中，等待气压抽至1×10-4Pa以下后，将衬底温度提升至190℃，待衬底温度达到稳定状态，再通过调节腔体中硼烷、氢气及硅烷的浓度(流量分别为1.5sccm、100sccm、10sccm)，制备厚度为30nm的P型非晶硅薄膜，沉积时间为15min，极板间距为10cm，所需功率密度为0.1mW/cm²。Step 3: Prepare the P-type layer using PECVD technology. Put the cleaned ITO glass substrate into the vacuum chamber, wait for the air pressure to be pumped below 1×10-4Pa, raise the substrate temperature to 190°C, wait for the substrate temperature to reach a stable state, and then adjust the chamber by adjusting the temperature of the substrate. The concentrations of borane, hydrogen and silane (the flow rates are 1.5sccm, 100sccm, and 10sccm, respectively), to prepare a P-type amorphous silicon film with a thickness of 30nm, the deposition time is 15min, the plate spacing is 10cm, and the required power density is 0.1mW /cm² .

步骤4：使用PECVD技术制备本征层。通过机械臂将衬底转移到本征层制备腔体中，等待气压抽至1×10^-4Pa以下后，将样品衬底温度提升至300℃，待衬底温度达到稳定状态。调节纯硅烷、氢气和H稀释比为1％的锗烷组成的气体(流量为50sccm)。衬底温度为300℃，极板间距10cm，馈入功率密度0.2mW/cm²,通过控制氢气、硅烷、锗烷流量的大小改变实验过程中锗的馈入比例，从而调节薄膜中的硅锗比例。Step 4: Prepare the intrinsic layer using PECVD technique. The substrate was transferred to the intrinsic layer preparation chamber by a robotic arm, and the temperature of the sample substrate was raised to 300°C after the air pressure was pumped below 1×10^-4 Pa, and the substrate temperature reached a stable state. A gas composed of pure silane, hydrogen, and germane with a dilution ratio of 1% H (flow rate 50 sccm) was adjusted. The substrate temperature is 300 °C, the distance between the plates is 10 cm, and the feeding power density is 0.2 mW/cm² . By controlling the flow rates of hydrogen, silane, and germane, the feeding ratio of germanium is changed during the experiment, so as to adjust the silicon germanium in the film. Proportion.

步骤5：使用PECVD技术制备N型层。将衬底转移到N型层制备腔体中，等待气压抽至1×10^^-4Pa以下后，将样品衬底温度提升至190℃，待衬底温度达到稳定状态，通过调节腔体中磷烷、氢气及硅烷的浓度(流量分别为2.0sccm、100sccm、10sccm)，制备厚度为30nm厚度的N型非晶硅薄膜，沉积时间为15min，极板间距为10cm，所需功率密度为0.1mW/cm²。Step 5: Prepare the N-type layer using PECVD technology. Transfer the substrate to the N-type layer preparation chamber, wait for the air pressure to be pumped below 1 × 10^^-4 Pa, increase the temperature of the sample substrate to 190 °C, and wait for the substrate temperature to reach a stable state. The concentrations of phosphine, hydrogen and silane (the flow rates are 2.0sccm, 100sccm, and 10sccm, respectively), to prepare an N-type amorphous silicon film with a thickness of 30nm, the deposition time is 15min, the distance between the plates is 10cm, and the required power density is 0.1 mW/cm² .

步骤6：使用热蒸发技术制备背电极。在冷却后的衬底上制备Ag背电极，背电极与N型层接触，厚度为200nm。Step 6: Preparation of back electrode using thermal evaporation technique. An Ag back electrode was prepared on the cooled substrate, and the back electrode was in contact with the N-type layer with a thickness of 200 nm.

2.制备第二隧穿结，具体步骤如下。2. The second tunneling junction is prepared, and the specific steps are as follows.

步骤7：使用电子束蒸发技术制备第二隧穿结。在硅-锗底电池上制备ITO第二隧穿结，ITO与P型层接触，厚度为200nm。Step 7: Fabrication of the second tunneling junction using electron beam evaporation techniques. The ITO second tunnel junction was fabricated on the silicon-germanium bottom cell, and the ITO was in contact with the P-type layer with a thickness of 200 nm.

3.制备窄带隙钙钛矿中间电池，包括第三载流子传输层、窄带隙钙钛矿层和第四载流子传输层，具体步骤如下。3. Prepare a narrow-bandgap perovskite intermediate cell, including a third carrier transport layer, a narrow-bandgap perovskite layer and a fourth carrier transport layer, and the specific steps are as follows.

步骤8：使用热蒸发技术制备第四载流子传输层，本实施例中的第四载流子层为电子传输层。把电池放入蒸发腔体内，在第二隧穿结上制备C60电子传输层，厚度为30nm。Step 8: Prepare a fourth carrier transport layer using thermal evaporation technology, the fourth carrier layer in this embodiment is an electron transport layer. Put the battery into the evaporation chamber, and prepare a C60 electron transport layer on the second tunnel junction with a thickness of 30 nm.

步骤9：使用旋涂法制备窄带隙钙钛矿光吸收层。在C₆₀层上旋涂窄带隙钙钛矿层FA_0.85Cs_0.15PbI_2.85Br_0.15，反溶剂为乙酸乙酯，反溶剂加入的量为300μl，并在105℃的条件下退火15min，该层厚度为600nm。Step 9: Fabrication of a narrow bandgap perovskite light absorbing layer using spin coating. A narrow bandgap perovskite layer FA_0.85 Cs_0.15 PbI_2.85 Br_0.15 was spin-coated on the C₆₀ layer, the anti-solvent was ethyl acetate, the amount of anti-solvent added was 300 μl, and annealed at 105 °C for 15 min, the layer thickness was 600nm.

步骤10：使用旋涂法制备第三载流子传输层，本实施例中的第三载流子传输层为空穴传输层。在窄带隙钙钛矿层上旋涂PEDOT：PSS，并在120℃的条件下退火20min，该层厚度为10nm。Step 10 : preparing a third carrier transport layer by spin coating, the third carrier transport layer in this embodiment is a hole transport layer. PEDOT:PSS was spin-coated on the narrow-bandgap perovskite layer and annealed at 120 °C for 20 min with a thickness of 10 nm.

4.制备第一隧穿结，具体步骤如下。4. The first tunneling junction is prepared, and the specific steps are as follows.

步骤11：使用ALD技术制备第一隧穿结。在窄带隙钙钛矿中间电池上制备SnO₂第一隧穿结，SnO₂与第三载流子传输层接触，厚度为200nm。Step 11: A first tunneling junction is fabricated using ALD technology. The first tunneling junction of_SnO2 was fabricated on a narrow-bandgap perovskite intermediate cell, and the_SnO2 was in contact with the third carrier transport layer with a thickness of 200 nm.

5.制备宽带隙钙钛矿顶电池，包括上电极、第一载流子传输层、宽带隙钙钛矿层和第二载流子传输层，具体步骤如下。5. The preparation of a wide-bandgap perovskite top cell includes an upper electrode, a first carrier transport layer, a wide-bandgap perovskite layer and a second carrier transport layer, and the specific steps are as follows.

步骤12：使用热蒸发技术制备第二载流子传输层，本实施例中的第二载流子层为电子传输层。把电池放入蒸发腔体内，在第一隧穿结上制备C₆₀电子传输层，厚度为40nm。Step 12 : using thermal evaporation technology to prepare a second carrier transport layer, the second carrier layer in this embodiment is an electron transport layer. The cell was put into the evaporation chamber, and a C₆₀ electron transport layer was prepared on the first tunnel junction with a thickness of 40 nm.

步骤13：使用旋涂法制备宽带隙钙钛矿光吸收层。在C₆₀上旋涂宽带隙钙钛矿CsPbIBr₂，反溶剂为氯苯，氯苯加入的量为350μl，并于105℃的条件下退火15min，其厚度为600nm。Step 13: A wide-bandgap perovskite light-absorbing layer is fabricated using spin coating. The wide-bandgap perovskite CsPbIBr₂ was spin-coated on C₆₀ , the anti-solvent was chlorobenzene, and the amount of chlorobenzene added was 350 μl, and annealed at 105 °C for 15 min with a thickness of 600 nm.

步骤14：使用旋涂法制备第一载流子传输层，本实施例中的第一载流子传输层为空穴传输层。在宽带隙钙钛矿层上旋涂PTAA，并在100℃的条件下退火20min，该层厚度为5nm。Step 14 : using spin coating to prepare a first carrier transport layer, the first carrier transport layer in this embodiment is a hole transport layer. PTAA was spin-coated on the wide-bandgap perovskite layer and annealed at 100 °C for 20 min with a thickness of 5 nm.

步骤15：使用电子束蒸发法制备ITO上电极，上电极与第一载流子传输层相接触，厚度为70nm；再使用丝网印刷法在上电极表面制备栅线电极，细栅线的宽度为35μm，栅线的间距为0.45cm。Step 15: Prepare the ITO upper electrode by electron beam evaporation, the upper electrode is in contact with the first carrier transport layer, and the thickness is 70 nm; then use the screen printing method to prepare grid line electrodes on the surface of the upper electrode, the width of the thin grid lines is 35 μm, and the pitch of the grid lines is 0.45 cm.

实施例2：Example 2:

一种高效的钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池，同实施例1相比区别是使用FA_0.5MA_0.5Pb_0.5Sn_0.5I₃作为窄带隙钙钛矿光吸收层。A high-efficiency perovskite/perovskite/silicon-germanium triple junction solar cell, the difference compared with Example 1 is that FA_0.5 MA_0.5 Pb_0.5 Sn_0.5 I₃ is used as a narrow bandgap perovskite light absorption layer .

采用步骤1～8制备钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池的其他各层。The other layers of the perovskite/perovskite/silicon-germanium triple junction tandem solar cell are prepared using steps 1-8.

步骤16：使用旋涂法制备窄带隙钙钛矿光吸收层。在C₆₀层上旋涂窄带隙钙钛矿层FA_0.5MA_0.5Pb_0.5Sn_0.5I₃，反溶剂为氯苯，反溶剂加入的量为300μl，并在105℃的条件下退火15min，该层厚度为800nm。Step 16: Prepare a narrow bandgap perovskite light absorbing layer using spin coating. A narrow bandgap perovskite layer FA_0.5 MA_0.5 Pb_0.5 Sn_0.5 I₃ was spin-coated on the C₆₀ layer, the anti-solvent was chlorobenzene, the amount of anti-solvent added was 300 μl, and annealed at 105 °C for 15 min, the thickness of the layer was is 800nm.

采用步骤10～15制备其余各层。Use steps 10-15 to prepare the remaining layers.

实施例3：Example 3:

一种高效的钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池，同实施例1和实施例2相比区别是使用FA_0.5MA_0.5Pb_0.5Sn_0.5I₃作为窄带隙钙钛矿光吸收层，使用FA_0.85Cs_0.15PbI_2.85Br_0.15作为宽带隙钙钛矿光吸收层.A high-efficiency perovskite/perovskite/silicon-germanium triple junction solar cell, the difference compared with Example 1 and Example 2 is that FA_0.5 MA_0.5 Pb_0.5 Sn_0.5 I₃ is used as a narrow bandgap perovskite FA_0.85 Cs_0.15 PbI_2.85 Br_0.15 was used as the wide bandgap perovskite light absorbing layer.

采用步骤1～8制备钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池。The perovskite/perovskite/silicon-germanium triple junction tandem solar cells are prepared by using steps 1-8.

采用步骤16制备窄带隙钙钛矿光吸收层。Step 16 is used to prepare a narrow bandgap perovskite light absorbing layer.

采用步骤10～12制备钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池。Steps 10-12 are used to prepare a perovskite/perovskite/silicon-germanium triple junction tandem solar cell.

采用步骤13制备宽带隙钙钛矿光吸收层。Step 13 is used to prepare the wide band gap perovskite light absorbing layer.

采用步骤14～15制备上电极和栅线电极。Steps 14-15 are used to prepare the upper electrode and the gate line electrode.

性能测试对比：Performance test comparison:

分别对实施例1、实施例2和实施例3提供的钙钛矿/钙钛矿/硅-锗三结叠层太阳能电池进行性能测试，结果如表2所示。The perovskite/perovskite/silicon-germanium triple junction tandem solar cells provided in Example 1, Example 2 and Example 3 were respectively tested for performance, and the results are shown in Table 2.

表2 实施例光电转化效率比较Table 2 Comparison of Photoelectric Conversion Efficiency of Examples

尽管已描述了本实用新型的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本实用新型范围的所有变更和修改。While the preferred embodiments of the present invention have been described, additional changes and modifications to these embodiments may occur to those skilled in the art once the basic inventive concepts are known. Therefore, the appended claims are intended to be construed to include the preferred embodiment and all changes and modifications that fall within the scope of this invention.

显然，本领域的技术人员可以对本实用新型进行各种改动和变型而不脱离本实用新型的精神和范围。这样，倘若本实用新型的这些修改和变型属于本实用新型权利要求及其等同技术的范围之内，则本实用新型也意图包含这些改动和变型在内。Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present utility model fall within the scope of the claims of the present utility model and their equivalents, the present utility model is also intended to include these modifications and variations.

Claims (8)

1. The perovskite/silicon-germanium-based triple-junction laminated solar cell is characterized by comprising a back electrode, a silicon-germanium bottom cell, a narrow-bandgap perovskite cell, a wide-bandgap perovskite cell and an upper electrode which are sequentially laminated, wherein the wide-bandgap perovskite top cell, the narrow-bandgap perovskite cell and the silicon-germanium bottom cell are arranged in series, the wide-bandgap perovskite cell and the narrow-bandgap perovskite cell are connected through a first tunneling junction, and the narrow-bandgap perovskite cell and the silicon-germanium bottom cell are connected through a second tunneling junction.

2. The solar cell according to claim 1, wherein the Si-Ge bottom cell comprises a first doped layer, an intrinsic layer and a second doped layer stacked in sequence, the intrinsic layer is a SiGe alloy layer, the intrinsic layer has a thickness of 400-600 nm, and the intrinsic layer has a bandgap of 0.67-1.12 eV.

3. The solar cell of claim 2, wherein the first and second doped layers are P-type and N-type layers, or N-type and P-type layers, respectively; the thickness of the first doping layer is 30-60 nm, and the thickness of the second doping layer is 30-60 nm.

4. The solar cell according to claim 1, wherein the wide bandgap perovskite solar cell comprises an upper electrode, a first carrier transport layer, a wide bandgap perovskite light absorption layer and a second carrier transport layer which are sequentially stacked, and the wide bandgap perovskite light absorption layer has a bandgap in a range of 1.7-2.1 eV.

5. The solar cell according to claim 1, wherein the narrow band gap perovskite solar cell comprises a third carrier transport layer, a narrow band gap perovskite light absorption layer and a fourth carrier transport layer which are sequentially stacked, and the band gap of the narrow band gap perovskite light absorption layer is in a range of 1.2-1.8 eV.

6. The solar cell according to any one of claims 1 to 5, wherein the first tunnel junction is a dense layer, and the dense layer is an N-type semiconductor material layer or a P-type semiconductor material layer.

7. The solar cell according to any one of claims 1 to 5, wherein the second tunnel junction is a metal oxide layer, and the metal oxide layer is one of a tin oxide layer, a titanium oxide layer, a zinc oxide layer, and an indium tin oxide layer.

8. The solar cell according to any one of claims 1 to 5, wherein the thickness of the first tunnel junction is 20nm to 300nm, and the thickness of the second tunnel junction is 20nm to 300 nm.

Images