CN101281935A - Measurement method of junction depth of silicon solar cell - Google Patents
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 48
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 210000004027 cell Anatomy 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 210000004692 intercellular junction Anatomy 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000004364 calculation method Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005305 interferometry Methods 0.000 description 1
- 208000001491 myopia Diseases 0.000 description 1
- 230000004379 myopia Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
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Abstract
本发明涉及一种硅太阳能电池结深的测量方法，属硅太阳能电池性能参数测量方法技术领域。本发明的测量方法采用了阳极氧化法结合差重计算法对硅太阳能电池的结深进行测量和计算。本发明的测量方法是：先测量未腐蚀的磷扩散层硅基片即电池片的重量及方块电阻，然后用阳极氧化法来氧化所述硅基片表面，得到了氧化层；然后用氢氟酸腐蚀掉所产生的氧化层，随后测量其方块电阻，重复多次上次操作，直到方块电阻由大变小时，称得其重量；这个重量与一开始称得重量的差值就是扩散层的重量，将这个重量差值除以扩散层的密度和腐蚀掉的扩散层的面积，就得到扩散层的平均深度，也即就是电池片的结深。
The invention relates to a method for measuring the junction depth of silicon solar cells, belonging to the technical field of measurement methods for performance parameters of silicon solar cells. The measurement method of the invention adopts the anodic oxidation method combined with the differential weight calculation method to measure and calculate the junction depth of the silicon solar cell. The measuring method of the present invention is: first measure the weight and sheet resistance of the uncorroded phosphorus diffusion layer silicon substrate, that is, the battery sheet, then use anodic oxidation to oxidize the surface of the silicon substrate to obtain an oxide layer; Acid corrodes the resulting oxide layer, then measures its sheet resistance, repeats the last operation several times until the sheet resistance changes from large to small, and weighs its weight; the difference between this weight and the weight weighed at the beginning is the diffusion layer. Weight, divide this weight difference by the density of the diffusion layer and the area of the etched diffusion layer to get the average depth of the diffusion layer, that is, the junction depth of the cell.
Description
技术领域technical field
本发明涉及一种硅太阳能电池结深的测量方法，属硅太阳能电池性能参数测量方法技术领域。The invention relates to a method for measuring the junction depth of silicon solar cells, belonging to the technical field of measurement methods for performance parameters of silicon solar cells.
背景技术Background technique
在能源逐渐匮乏的当今社会，人们急需找到一种可再生能源来代替非可再生能源。众所周知，太阳给了地球无穷无尽地热量，因此人们把目标指向了太阳。In today's society where energy is gradually scarce, people urgently need to find a renewable energy to replace non-renewable energy. As we all know, the sun gives the earth endless heat, so people point their targets at the sun.
对于硅太阳电池的制作，p-n结是电池的“心脏”，之所以太阳电池能够产生电是利用p-n结的静电场作用，将电子和空穴对分离，电子集中在一边，空穴集中在另一边，从而达到发电的目的，所以p-n结的好坏将直接影响到太阳电池性能的好坏。在硅太阳能电池的生产过程中，一般采用磷源扩散法，即用氮气携带三氯氧磷，在高温和有氧环境下，通过置换反应，进而扩散入硅片内。扩散的深度也就是结深是对太阳能电池的效率影响很大，结深太深或者太浅都会减少载流子的寿命，影响其效率，想要提高电池的效率就必须有适当的结深。而控制结深的前提就是能够测量结深。目前测量结深的方法大都来自测量抛光芯片结深的方法，如显色法，干涉法等。可是太阳能电池相对于抛光芯片来说具有其自身的特点，那就是：For the production of silicon solar cells, the p-n junction is the "heart" of the battery. The reason why solar cells can generate electricity is to use the electrostatic field of the p-n junction to separate electrons and holes. The electrons are concentrated on one side, and the holes are concentrated on the other side. On the one hand, so as to achieve the purpose of power generation, so the quality of the p-n junction will directly affect the performance of the solar cell. In the production process of silicon solar cells, the phosphorus source diffusion method is generally adopted, that is, phosphorus oxychloride is carried by nitrogen gas, and then diffused into the silicon wafer through displacement reaction under high temperature and aerobic environment. The depth of diffusion, that is, the junction depth, has a great influence on the efficiency of solar cells. If the junction depth is too deep or too shallow, it will reduce the life of carriers and affect its efficiency. To improve the efficiency of the cell, it is necessary to have an appropriate junction depth. The premise of controlling the junction depth is to be able to measure the junction depth. At present, most of the methods for measuring the junction depth come from the method of measuring the junction depth of polished chips, such as chromogenic method and interferometry. However, solar cells have their own characteristics compared to polished chips, that is:
1、它的结深比较浅，小于0.5微米。1. Its junction depth is relatively shallow, less than 0.5 microns.
2、在其表面，由于要减少光的反射，所以呈绒面或金字塔型结构，金字塔的高度为2～4微米。2. On its surface, due to the need to reduce the reflection of light, it has a suede or pyramid structure, and the height of the pyramid is 2 to 4 microns.
扩散的过程中，平常的芯片的PN结是水平的，芯片表面是抛光的，而对硅太阳能电池来说，磷原子从金字塔的侧面扩散进入硅片，这就给测量造成了一定的困难，基于这些特点，就必须寻找新的方法来测量结深。During the diffusion process, the PN junction of ordinary chips is horizontal and the chip surface is polished, but for silicon solar cells, phosphorus atoms diffuse into the silicon chip from the side of the pyramid, which causes certain difficulties for measurement. Based on these characteristics, it is necessary to find a new method to measure the junction depth.
发明内容Contents of the invention
本发明采用了阳极氧化法结合差重法对硅太阳能电池的结深进行测量。The invention adopts the anodic oxidation method combined with the differential gravity method to measure the junction depth of the silicon solar cell.
本发明一种硅太阳能电池结深的测量方法，其特征在于具有以下的步骤：A method for measuring the depth of a silicon solar cell junction of the present invention is characterized in that it has the following steps:
a.将具有磷扩散层的硅基片的硅太阳能电池作为测试对象；首先用超声波清洗磷扩散层硅基片，然后用氢氟酸腐蚀掉磷扩散时残留的原始氧化层；此时测量所述磷扩散层硅基片也即电池片的重量及方块电阻；a. The silicon solar cell with the silicon substrate of the phosphorus diffusion layer is used as the test object; first, the silicon substrate of the phosphorus diffusion layer is cleaned with ultrasonic waves, and then the residual original oxide layer is etched away when the phosphorus is diffused with hydrofluoric acid; The silicon substrate of the phosphorus diffusion layer is also the weight and the sheet resistance of the battery sheet;
b.接着用阳极氧化法来氧化硅基片表面；氧化1分钟后用氢氟酸腐蚀掉产生的氧化层，随后测量其方块电阻；再氧化，再测量，如此重复多次后，会发现方块电阻由逐渐变大突然转为变小；到方块电阻变小时称得其重量；这个重量与一开始称得的重量的差值就是扩散层的重量；将这个重量差值除以扩散层的密度和腐蚀掉的扩散层的面积，就得到扩散层的平均深度，也即就是电池片的结深。b. Then use the anodic oxidation method to oxidize the surface of the silicon substrate; after oxidizing for 1 minute, use hydrofluoric acid to corrode the resulting oxide layer, and then measure its sheet resistance; re-oxidize and measure again, after repeating this many times, you will find a square The resistance changes from gradually increasing to suddenly decreasing; when the square resistance becomes smaller, its weight is weighed; the difference between this weight and the weight weighed at the beginning is the weight of the diffusion layer; divide this weight difference by the density of the diffusion layer and the area of the etched diffusion layer, the average depth of the diffusion layer is obtained, that is, the junction depth of the cell.
所述的阳极氧化法是以铜片为阴极，硅基片也即电池片为阳极，电解液为硝酸钠溶液；电源为60±15V的直流电源。In the anodic oxidation method, a copper sheet is used as a cathode, a silicon substrate, that is, a battery sheet, is used as an anode, the electrolyte is a sodium nitrate solution, and the power supply is a 60±15V DC power supply.
本发明测量太阳能电池结深的原理如下：The principle of measuring solar cell junction depth in the present invention is as follows:
由于硅太阳能电池的PN结不是水平方向的，而且硅基片表面的状态不利于直接观察结深，因此只有间接测量。这里选用阳极氧化法是因为这种方法氧化硅片的速度较慢，适用于浅结的测量，能精确地腐蚀掉扩散层，即便会腐蚀掉少许衬底，但此方法测量结深的误差小于300埃。同时可避免热氧化法制得氧化层带来的使扩散层变深的后果。先测量未腐蚀的电池片的重量，然后测量腐蚀掉扩散层的电池片的重量，两者的差值就是扩散层的重量，再用这个重量除以扩散层的密度和腐蚀掉的扩散层的面积(整个电池片的表面积，为金字塔的侧面积总和)就得出扩散层的深度，也就是平均结深。Since the PN junction of silicon solar cells is not horizontal, and the state of the surface of the silicon substrate is not conducive to directly observing the junction depth, only indirect measurement is possible. The reason why the anodic oxidation method is used here is that the speed of silicon wafer oxidation is relatively slow, which is suitable for the measurement of shallow junctions, and can accurately corrode the diffusion layer. 300 Angstroms. At the same time, it can avoid the consequence of deepening the diffusion layer caused by the oxide layer produced by the thermal oxidation method. First measure the weight of the uncorroded cell, and then measure the weight of the cell with the diffusion layer corroded. The difference between the two is the weight of the diffusion layer, and then divide this weight by the density of the diffusion layer and the density of the corroded diffusion layer. The area (the surface area of the entire cell, which is the sum of the side areas of the pyramid) gives the depth of the diffusion layer, which is the average junction depth.
本发明方法不同于平常的抛光芯片表面积结深的测量，因平常抛光芯片的PN结是水平的；而本发明的特点是可以测量硅太阳能电池片的金字塔型表面的结深。The method of the present invention is different from the measurement of the junction depth of the surface area of the ordinary polished chip, because the PN junction of the ordinary polished chip is horizontal; and the feature of the present invention is that the junction depth of the pyramidal surface of the silicon solar cell can be measured.
附图说明Description of drawings
图1为本发明中用阳极氧化法来氧化硅基片表面的装置的示意图。Fig. 1 is the schematic diagram of the device for oxidizing the surface of silicon substrate by anodic oxidation method in the present invention.
图2为具有磷扩散层硅基片绒面表面的氧化示意图。Fig. 2 is a schematic diagram of the oxidation of the textured surface of a silicon substrate with a phosphorus diffusion layer.
具体实施方式Detailed ways
现将本发明的具体实施例叙述于后。Specific embodiments of the present invention are described below.
实施例1Example 1
本实施例中硅太阳能电池的结深的测量方法的步骤如下：The steps of the method for measuring the junction depth of silicon solar cells in this embodiment are as follows:
(1)将硅太阳能电池的电池片，也即具有磷扩散层的硅基片先进行超声波清洗，然后用氢氟酸腐蚀掉磷扩散时残留的原始氧化层；此时测量所述磷扩散层硅基片也即电池片的重量M1及其方块电阻；(1) The cells of the silicon solar cell, that is, the silicon substrate with the phosphorus diffusion layer, are first ultrasonically cleaned, and then the original oxide layer remaining when the phosphorus is diffused is corroded with hydrofluoric acid; at this time, the phosphorus diffusion layer is measured The silicon substrate is also the weight M1 of the cell and its sheet resistance;
(2)接着用阳极氧化法来氧化硅基片表面；氧化装置参见图1；图1为用阳极氧化法来氧化所述硅基片表面的装置示意图。以铜为阴极，以所述硅基片也即电池片为阳极，电解液为硝酸钠溶液，在直流电源电压为65V的条件下进行阳极氧化反应；氧化反应1分钟后得到氧化层，并用氢氟酸腐蚀掉产生的氧化层，随后测量其方块电阻；再氧化，再测量，如此重复9次后，过程中会发现方块电阻由逐渐变大突然转为变小；到方块电阻变小时称得其重量M2；将该重量M2与一开始称得的重量M1的差值即(M1-M2)，即就是扩散层的重量；将这个重量差值除以扩散层的密度和腐蚀掉的扩散层的面积，就得到扩散层的平均深度，也即就是所述电池片的结深。(2) Then use the anodic oxidation method to oxidize the surface of the silicon substrate; refer to Fig. 1 for the oxidation device; Fig. 1 is a schematic diagram of the device for oxidizing the surface of the silicon substrate by the anodic oxidation method. Copper is used as the cathode, the silicon substrate, that is, the battery sheet, is used as the anode, the electrolyte is sodium nitrate solution, and the anodic oxidation reaction is carried out under the condition of a DC power supply voltage of 65V; the oxidation layer is obtained after 1 minute of oxidation reaction, and the hydrogen Hydrofluoric acid corrodes the generated oxide layer, and then measures its sheet resistance; re-oxidizes and measures again, and after repeating this 9 times, it will be found that the sheet resistance changes from gradually increasing to suddenly decreasing; when the sheet resistance becomes smaller, it is called Its weight M 2 ; the difference between the weight M 2 and the initially weighed weight M 1 is (M 1 -M 2 ), that is, the weight of the diffusion layer; divide this weight difference by the density of the diffusion layer and The area of the etched diffusion layer is the average depth of the diffusion layer, that is, the junction depth of the battery sheet.
其计算公式为：
此处：A为面积因子，取值范围为1.0～1.8；L为电池片的长度，W为电池片的謇度，Psi为硅扩散层的密度。Here: A is the area factor, and the value range is 1.0 to 1.8; L is the length of the cell, W is the stiffness of the cell, and P si is the density of the silicon diffusion layer.
扩散层的面积应是整个电池片的表面积，即应是金字塔型表面的测量面积的总和，在本公式中仅是近视计算的表面积。The area of the diffusion layer should be the surface area of the entire cell, that is, the sum of the measured areas of the pyramid-shaped surfaces, which is only the surface area calculated by myopia in this formula.
本实施例的测试结果见下表1。The test results of this embodiment are shown in Table 1 below.
表1本实施例的测试结果The test result of table 1 present embodiment
本发明的测量方法在测试过程中应注意之点如下：The points that should be noted during the testing process of the measuring method of the present invention are as follows:
在腐蚀过程中只能把氢氟酸涂布在扩散层那一面，而不能把整个测试样品浸入氟酸内；因为硅太阳能电池的电池片背面也是硅材料，同样可以被氧化，产生氧化层，如果把样品浸入氢氟酸内，同样会腐蚀掉这一层，最终影响测量的准确性。因此，为了提高准确性，只能腐蚀掉扩散层所在的那一面产生的氧化层。During the corrosion process, hydrofluoric acid can only be coated on the side of the diffusion layer, and the entire test sample cannot be immersed in hydrofluoric acid; because the back of the silicon solar cell is also a silicon material, which can also be oxidized to produce an oxide layer. If the sample is immersed in hydrofluoric acid, this layer will also be corroded, which will eventually affect the accuracy of the measurement. Therefore, in order to improve accuracy, only the oxide layer produced on the side where the diffusion layer is located can be etched away.
关于具有磷扩散层硅基层绒面表面即金字塔型表面的氧化情况参见图2。Refer to FIG. 2 for the oxidation of the silicon-based suede surface with the phosphorus diffusion layer, that is, the pyramid-shaped surface.
本发明的测量方法可应用于测量太阳能硅电池的结深，为扩散工艺提供所需的数据信息，对于控制和改善扩散工艺，提高太阳能电池的效率是有积极意义的。The measurement method of the invention can be applied to measure the junction depth of solar silicon cells, provide required data information for diffusion process, and have positive significance for controlling and improving diffusion process and improving the efficiency of solar cells.
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| CN102243984B (en) * | 2010-05-11 | 2013-05-08 | 扬州杰利半导体有限公司 | Method of removing boron spots on chip |
| CN101833069A (en) * | 2010-05-14 | 2010-09-15 | 沈阳汉锋新能源技术有限公司 | Detection device of thin film conversion rate |
| CN102818980A (en) * | 2012-08-13 | 2012-12-12 | 安阳市凤凰光伏科技有限公司 | Method for testing quality of silicon substrate in solar battery |
| CN103996635A (en) * | 2014-05-16 | 2014-08-20 | 中山大学 | A method for detecting the uniformity of solar cell diffusion |
| CN103996635B (en) * | 2014-05-16 | 2017-08-11 | 中山大学 | A kind of method for detecting diffusion uniformity of solar battery |
| CN109360784A (en) * | 2018-09-13 | 2019-02-19 | 安徽钜芯半导体科技有限公司 | A method of removal chip surface Pyrex |
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