CN111261788B - Manufacturing method of solar cell and method for preparing shell layer by using sol method - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000012792 core layer Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000002070 nanowire Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 35
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 239000011257 shell material Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000004308 accommodation Effects 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及太阳能电池技术领域，特别是涉及一种太阳能电池的制作方法及溶胶法制备壳层的方法。The invention relates to the technical field of solar cells, in particular to a method for manufacturing a solar cell and a method for preparing a shell layer by a sol method.
背景技术Background technique
以钙钛矿材料为壳，传输材料为芯层的纳米线用于太阳能电池有望获得高光电转换效率。目前，传统的壳芯结构纳米线阵列均为直立状结构，若将以钙钛矿材料为吸光层的壳芯结构钙钛矿纳米线阵列应用于太阳能电池，则太阳光需从电池的侧面入射，影响器件的使用性能。Nanowires with perovskite materials as the shell and transport materials as the core layer are expected to obtain high photoelectric conversion efficiency when used in solar cells. At present, the traditional shell-core structure nanowire arrays are all upright structures. If the shell-core structure perovskite nanowire arrays with perovskite materials as the light-absorbing layer are applied to solar cells, sunlight needs to be incident from the side of the cell. , affecting the performance of the device.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种太阳能电池的制作方法及溶胶法制备壳层的方法，太阳光无须从侧面入射而可以直接从电池的正面入射，从而提高器件效率，这将使得其十分适合于智能穿戴等领域。The purpose of the present invention is to overcome the deficiencies in the prior art, to provide a method for manufacturing a solar cell and a method for preparing a shell layer by a sol method. The sunlight does not need to be incident from the side but can be directly incident from the front of the battery, thereby improving device efficiency. It will make it very suitable for smart wear and other fields.
本发明的目的是这样实现的：The purpose of the present invention is achieved like this:
一种平铺式壳芯结构钙钛矿纳米线的壳层制作方法，包括以下步骤：A method for manufacturing a shell layer of a tiled shell-core structure perovskite nanowire, comprising the following steps:
a、准备衬底，所述衬底上具有平铺阵列式的芯层，所述衬底、芯层的亲疏水性相反；a. Prepare the substrate, which has a tiled array core layer, and the substrate and the core layer have opposite hydrophilicity and hydrophobicity;
b、向钙钛矿溶胶中加入溶剂，配制出壳层溶胶，所述溶剂的亲疏水性与芯层的亲疏水性相同；b. Adding a solvent to the perovskite sol to prepare a shell sol, the hydrophilicity and hydrophobicity of the solvent are the same as those of the core layer;
c、将具有芯层的衬底放入壳层溶胶中浸泡，经烘干、退火后，构筑出壳芯结构纳米线阵列。c. Soaking the substrate with the core layer in the shell sol, drying and annealing, constructing a shell-core structure nanowire array.
优选地，所述衬底的材料为疏水性材料，所述芯层的材料为亲水性材料，所述溶剂为亲水性溶剂。Preferably, the material of the substrate is a hydrophobic material, the material of the core layer is a hydrophilic material, and the solvent is a hydrophilic solvent.
优选地，所述衬底的材料为硅片或PVDF，所述芯层的材料为二氧化钛，所述溶剂采用十二烷二酸。Preferably, the material of the substrate is silicon wafer or PVDF, the material of the core layer is titanium dioxide, and the solvent is dodecanedioic acid.
优选地，所述衬底的材料为亲水性材料，所述芯层的材料为疏水性材料，所述溶剂为疏水性溶剂。Preferably, the material of the substrate is a hydrophilic material, the material of the core layer is a hydrophobic material, and the solvent is a hydrophobic solvent.
优选地，所述衬底的材料为PET，所述芯层的材料为NMPFP，所述溶剂采用邻二氯苯或氯苯。Preferably, the material of the substrate is PET, the material of the core layer is NMPFP, and the solvent is o-dichlorobenzene or chlorobenzene.
一种平铺式壳芯结构钙钛矿纳米线太阳能电池的制作方法，包括以下步骤：A method for making a flat shell-core structure perovskite nanowire solar cell, comprising the following steps:
S1、在衬底的一端设置第一电极；S1, setting a first electrode at one end of the substrate;
S2、在衬底上制备芯层；S2, preparing a core layer on the substrate;
S3、在芯层上制备壳层；S3, preparing a shell layer on the core layer;
S4、在衬底的另一端设置第二电极。S4, setting a second electrode on the other end of the substrate.
优选地，步骤S3中：具有芯层的衬底背向第一电极的一端放入壳层溶胶中浸泡，壳层溶胶的液面与第一电极之间留有间距。Preferably, in step S3: the end of the substrate with the core layer facing away from the first electrode is immersed in the shell sol, and a distance is left between the liquid surface of the shell sol and the first electrode.
由于采用了上述技术方案，平铺式壳芯结构钙钛矿纳米线太阳能电池具有如下有益效果：Due to the adoption of the above-mentioned technical scheme, the tiled shell-core structure perovskite nanowire solar cell has the following beneficial effects:
(1)减反射，聚光能力强；(1) Anti-reflection, strong light-gathering ability;
(2)体积小，利于器件的小型化；(2) Small size, which is conducive to the miniaturization of devices;
(3)柔性好，适于制备柔性器件；(3) Good flexibility, suitable for preparing flexible devices;
(4)易单晶化，可降低电子-空穴复合率；(4) Easy single crystallization, which can reduce the electron-hole recombination rate;
(5)更适于输运载流子，增大载流子扩散强度及寿命等。(5) It is more suitable for transporting carriers, increasing the diffusion strength and lifetime of carriers, etc.
由于纳米线具有这些优势，将其应用于太阳能电池中有望获得高光电转换效率；且由于它同时具有柔性及小型化的优点，使其适用于智能穿戴设备。而考虑到智能穿戴设备的一个正常使用情况，需要太阳光从其正面入射，因此，平铺状的壳芯结构钙钛矿纳米线阵列型太阳能电池可满足智能穿戴设备等柔性器件的用电需求，为其发展奠定基础。Due to these advantages of nanowires, it is expected to obtain high photoelectric conversion efficiency when applied to solar cells; and because it has the advantages of flexibility and miniaturization, it is suitable for smart wearable devices. Considering that a normal use of smart wearable devices requires sunlight to be incident from the front, therefore, flat shell-core structure perovskite nanowire array solar cells can meet the electricity demand of flexible devices such as smart wearable devices. , to lay the foundation for its development.
附图说明Description of drawings
图1为本发明电池的结构示意图；Fig. 1 is the structural representation of battery of the present invention;
图2为图1的俯视示意图；Fig. 2 is a top view schematic diagram of Fig. 1;
图3为图2的A-A剖视示意图；Fig. 3 is a schematic sectional view of A-A of Fig. 2;
图4为本发明制作方法的示意图。Fig. 4 is a schematic diagram of the manufacturing method of the present invention.
附图标记reference sign
附图中，1为衬底，2为第一电极，3为第二电极，4为芯层，5为壳层，6为模板。In the drawings, 1 is a substrate, 2 is a first electrode, 3 is a second electrode, 4 is a core layer, 5 is a shell layer, and 6 is a template.
具体实施方式Detailed ways
参见图1-图3，为一种平铺式壳芯结构钙钛矿纳米线太阳能电池，包括呈片状的衬底(采用绝缘材料)，所述衬底的两端分别电镀有呈条形的第一电极、第二电极，所述第一电极、第二电极相互平行，所述第一电极、第二电极之间沿平面阵列设置有若干壳芯结构钙钛矿纳米线，各壳芯结构钙钛矿纳米线相互平行，所述壳芯结构钙钛矿纳米线包括传输材料制成的芯层以及钙钛矿材料制成的壳层，所述芯层与第一电极连接，所述壳层与第二电极连接。Referring to Fig. 1-Fig. 3, it is a perovskite nanowire solar cell with flat shell-core structure, including a sheet-shaped substrate (using insulating material), and the two ends of the substrate are respectively electroplated with strip-shaped The first electrode and the second electrode, the first electrode and the second electrode are parallel to each other, a number of perovskite nanowires with shell-core structure are arranged between the first electrode and the second electrode along the plane array, and each shell core The structural perovskite nanowires are parallel to each other, and the shell-core structure perovskite nanowires include a core layer made of a transmission material and a shell layer made of a perovskite material, the core layer is connected to the first electrode, and the The shell layer is connected with the second electrode.
所述芯层设置在衬底上，芯层的一端与第一电极连接，所述壳层覆盖在芯层上，壳层的一端与第一电极之间留有间距，防止壳层与第一电极发生导电，壳层的另一端封住芯层，且与第二电极连接。所述第一电极嵌入衬底内，所述第一电极上固定有模板，所述芯层固定于模板上设置的凹槽内。The core layer is arranged on the substrate, one end of the core layer is connected to the first electrode, the shell layer is covered on the core layer, and a distance is left between one end of the shell layer and the first electrode to prevent the shell layer from contacting the first electrode. The electrode conducts electricity, and the other end of the shell layer seals the core layer and is connected to the second electrode. The first electrode is embedded in the substrate, a template is fixed on the first electrode, and the core layer is fixed in a groove provided on the template.
所述衬底、第一电极、第二电极、壳芯结构钙钛矿纳米线中的至少一种为柔性材料。更加满足智能穿戴设备等柔性器件的实用需求。平铺式壳芯结构钙钛矿纳米线太阳能电池应用于智能穿戴设备，非常适用于对智能穿戴设备供电。At least one of the substrate, the first electrode, the second electrode, and the core-shell perovskite nanowire is a flexible material. It better meets the practical needs of flexible devices such as smart wearable devices. The tiled shell-core structure perovskite nanowire solar cell is applied to smart wearable devices, and is very suitable for powering smart wearable devices.
一种平铺式壳芯结构钙钛矿纳米线的壳层制作方法，包括以下步骤：A method for manufacturing a shell layer of a tiled shell-core structure perovskite nanowire, comprising the following steps:
a、准备衬底，所述衬底上具有平铺阵列式的芯层，所述衬底、芯层的亲疏水性相反；a. Prepare the substrate, which has a tiled array core layer, and the substrate and the core layer have opposite hydrophilicity and hydrophobicity;
b、向钙钛矿溶胶中加入溶剂，配制出壳层溶胶，所述溶剂的亲疏水性与芯层的亲疏水性相同；b. Adding a solvent to the perovskite sol to prepare a shell sol, the hydrophilicity and hydrophobicity of the solvent are the same as those of the core layer;
c、将具有芯层的衬底放入壳层溶胶中浸泡，经烘干、退火后，构筑出壳芯结构纳米线阵列。c. Soaking the substrate with the core layer in the shell sol, drying and annealing, constructing a shell-core structure nanowire array.
利用材料的亲疏水特性，可以有效解决壳层材料铺满整个衬底的问题，从而有望获得高光电转换效率的壳/芯结构钙钛矿纳米线阵列型太阳能电池。Utilizing the hydrophilic and hydrophobic properties of the material can effectively solve the problem that the shell material covers the entire substrate, and it is expected to obtain a shell/core structure perovskite nanowire array solar cell with high photoelectric conversion efficiency.
一种实施方案为：所述衬底的材料为疏水性材料，所述芯层的材料为亲水性材料，所述溶剂为亲水性溶剂，亲水性溶剂比如二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、乙醚等。本实施例中，所述衬底的材料为硅片或PVDF(具有柔性)，所述芯层的材料为二氧化钛，所述溶剂采用十二烷二酸(DDDA)，DDDA的两端具有羧基，一端容易与二氧化钛(电子传输层-芯层)中的Ti4+接触，另一端羧基具有亲水性。One embodiment is: the material of the substrate is a hydrophobic material, the material of the core layer is a hydrophilic material, and the solvent is a hydrophilic solvent, and the hydrophilic solvent is such as dimethylformamide (DMF ), dimethyl sulfoxide (DMSO), ether, etc. In this embodiment, the material of the substrate is silicon wafer or PVDF (having flexibility), the material of the core layer is titanium dioxide, the solvent adopts dodecanedioic acid (DDDA), and the two ends of DDDA have carboxyl groups, One end is easy to contact with Ti4+ in titanium dioxide (electron transport layer-core layer), and the carboxyl group at the other end is hydrophilic.
另一种实施方案为：所述衬底的材料为亲水性材料，所述芯层的材料为疏水性材料，所述溶剂为疏水性溶剂。本实施例中，所述衬底的材料为PET(具有柔性)，所述芯层的材料为富勒烯衍生物N-甲基-2-戊基富勒烯吡咯烷(NMPFP)，所述溶剂采用邻二氯苯或氯苯。Another embodiment is: the material of the substrate is a hydrophilic material, the material of the core layer is a hydrophobic material, and the solvent is a hydrophobic solvent. In this embodiment, the material of the substrate is PET (flexible), the material of the core layer is the fullerene derivative N-methyl-2-pentylfullerene pyrrolidine (NMPFP), the The solvent adopts o-dichlorobenzene or chlorobenzene.
参见图4，一种平铺式壳芯结构钙钛矿纳米线太阳能电池的制作方法，包括以下步骤：Referring to Fig. 4, a method for manufacturing a perovskite nanowire solar cell with a tiled shell-core structure includes the following steps:
S1、在衬底的一端电镀上第一电极；S1. Electroplating a first electrode on one end of the substrate;
S2、在衬底上制备芯层；步骤S2包括：S2. Prepare a core layer on the substrate; Step S2 includes:
S21、准备模板，采用电子束曝光法在模板上刻蚀出凹槽，凹槽的槽宽为100nm左右；S21. Prepare a template, and etch a groove on the template by using an electron beam exposure method, and the groove width of the groove is about 100nm;
S22、将模板凹槽向下，并和衬底粘合固定在一起，凹槽与衬底之间形成芯层的容纳空间，再放入芯层溶胶中浸泡，直至芯层溶胶充满所述容纳空间；S22. Place the groove of the template downwards, and glue and fix it with the substrate. The accommodation space for the core layer is formed between the groove and the substrate, and then soaked in the core layer sol until the core layer sol fills the accommodation space. space;
S23、经烘干、退火后，保留第一电极上方的模板部分，去除其余模板部分，形成沿平面阵列的芯层。S23. After drying and annealing, retain the template portion above the first electrode, and remove the rest of the template portion to form a core layer arrayed along a plane.
S3、按上述方法在芯层上制备壳层；S3, preparing a shell layer on the core layer according to the above method;
S32、将具有芯层的衬底放入壳层溶胶中浸泡，经烘干、退火后，构筑出壳芯结构纳米线阵列。步骤S32中，具有芯层的衬底背向第一电极的一端放入壳层溶胶中浸泡，壳层溶胶的液面与第一电极之间留有间距。S32, soaking the substrate with the core layer in the shell sol, drying and annealing, and constructing a shell-core structure nanowire array. In step S32, the end of the substrate with the core layer facing away from the first electrode is immersed in the shell sol, and a distance is left between the liquid surface of the shell sol and the first electrode.
S4、在衬底的另一端电镀上第二电极。S4, plating a second electrode on the other end of the substrate.
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that it can be described in terms of form and Various changes may be made in the details without departing from the scope of the invention defined by the claims.
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