本文選題：兩步法制黑硅 + 金屬輔助化學(xué)刻蝕�。� 參考：《蘇州大學(xué)》2014年碩士論文

【摘要】：近幾年，黑硅作為一種具備納米陷光結(jié)構(gòu)的新型半導(dǎo)體光電材料，由于其在可見——紅外波段反射率極低，能夠有效的提高電池片的轉(zhuǎn)化效率，因而受到了人們的極大關(guān)注。制備黑硅的方法很多，其中金屬輔助化學(xué)刻蝕法由于所需設(shè)備簡(jiǎn)單、成本低、易于整合到目前太陽能電池生產(chǎn)工序中而備受人們青睞。目前已有許多小組在從事金屬輔助化學(xué)刻蝕方法的研究，也取得了一定的成果，但大多都采用一步法進(jìn)行實(shí)驗(yàn)。而一步法制黑硅存在兩方面的缺點(diǎn)：一方面，反應(yīng)過程消耗大量的重金屬Ag；另一方面，殘留過多的金屬粒子增加了后續(xù)清洗工作的負(fù)擔(dān)。 本文研發(fā)的全液相兩步法不僅可以與產(chǎn)線上現(xiàn)有制絨工藝很好的兼容，而且可以有效的解決一步法制黑硅的兩大弊端，這在很大程度上節(jié)約了生產(chǎn)成本，也簡(jiǎn)化了產(chǎn)線上的工藝步驟，所以研究?jī)刹椒ㄖ坪诠杈哂兄匾膶?shí)踐意義。 首先，兩步法制黑硅(TSM)是指應(yīng)用控制變量法先將制絨過的硅片先放到硝酸銀（催化劑）溶液中反應(yīng)一定時(shí)間，再放入適當(dāng)體積比的氫氟酸（刻蝕劑）和過氧化氫（氧化劑）混合溶液中反應(yīng)一段時(shí)間，制備出具有納米陷光的絨面結(jié)構(gòu)，即黑硅結(jié)構(gòu)。本文主要研究了三種溶液濃度以及反應(yīng)時(shí)間下的硅片絨面形貌，選用掃描電子顯微鏡（SEM）和光學(xué)顯微鏡（OM）對(duì)其進(jìn)行了表征。結(jié)果發(fā)現(xiàn)：不同的溶液濃度和反應(yīng)時(shí)間會(huì)得到納米線狀和孔洞狀兩種完全不同的結(jié)構(gòu)。 其次，本文通過SEM、EDX和粒徑分析軟件對(duì)兩步法與一步法制黑硅中Ag顆粒進(jìn)行了表征，結(jié)果發(fā)現(xiàn)：兩步法消耗非常少的重金屬，而且金屬粒子分布很均勻，顆粒大小也有一定的規(guī)律性。因?yàn)閮刹椒ǚ磻?yīng)消耗很少Ag，后續(xù)可以很徹底的將殘余的金屬粒子去除干凈，避免了電池片表面金屬殘余導(dǎo)致的復(fù)合。 最后，從結(jié)構(gòu)上來看兩步法制黑硅相當(dāng)于在原來微米結(jié)構(gòu)的基礎(chǔ)上又生長(zhǎng)了一種納米結(jié)構(gòu)，即形成了一種微納復(fù)合結(jié)構(gòu)，這樣就使得硅片的反射率由原來的25%左右降低到5%左右甚至更低。選用標(biāo)準(zhǔn)8度角絨面積分式反射儀（D8反射儀）對(duì)黑硅的光學(xué)性質(zhì)進(jìn)行了表征，并發(fā)現(xiàn)確實(shí)能夠獲得極低的反射率。然而，這種具有極低反射率的黑硅卻有很深的結(jié)構(gòu)，即很大的比表面積，會(huì)大大增加表面載流子復(fù)合中心數(shù)量，導(dǎo)致電池片的轉(zhuǎn)換效率下降。所以，我們?cè)谥仆旰诠柚蠹恿艘徊絼冸x修正，通過參數(shù)的調(diào)控可以將納米陷光結(jié)構(gòu)的深度控制在理想的范圍內(nèi)。本文將兩步法制完的多晶黑硅電池在蘇州阿特斯陽光電力科技有限公司做了流片分析，流片數(shù)據(jù)表明該類電池的平均效率為18.05%，高于產(chǎn)線17.52%的平均值。 綜上所述，我們?cè)趯?shí)驗(yàn)室和產(chǎn)線上證實(shí)了全液相兩步法金屬輔助化學(xué)刻蝕制備黑硅太陽能電池的可行性，，并且與一步法比較體現(xiàn)出了其較大優(yōu)勢(shì)。本文的研究?jī)?nèi)容可以在很大程度上促進(jìn)我國(guó)光伏產(chǎn)業(yè)的發(fā)展，全液相兩步法制黑硅技術(shù)存在巨大的實(shí)踐應(yīng)用潛力。
[Abstract]:In recent years, as a new type of semiconductor optoelectronic materials with nanometer trapping structure, black silicon has attracted great attention because of its low reflectance in the visible and infrared wavelengths, which can effectively improve the conversion efficiency of the battery. There are many ways to prepare the black silicon, in which the metal assisted chemical etching is the equipment needed. Simple, low cost, easy to integrate into the current production process of solar cells, it is very popular. At present, many groups have been engaged in the research of metal assisted chemical etching methods, and some achievements have been made. But most of them have been experimentation with one step method. There are two shortcomings in the one step process of black silicon. On the one hand, the reaction is over. The process consumes a large amount of heavy metal Ag; on the other hand, excessive residual metal particles increase the burden of subsequent cleaning.
The total liquid phase two step method developed in this paper can not only be compatible with the existing cashmere process in the production line, but also can effectively solve the two disadvantages of the one-step process of the black silicon. This saves the production cost to a great extent, and simplifies the process steps of the production line. Therefore, it is of great practical significance to study the two step method of black silicon.
First, the two step method of black silicon (TSM) is the application of the controlled variable method to first place the flush silicon chip in the silver nitrate (catalyst) solution for a certain time, then reacts in a mixed solution of hydrofluoric acid (etch) and hydrogen peroxide (oxidizer) in a proper volume ratio for a period of time to prepare a nanoscale suede structure, that is, black silicon. Structure. In this paper, three kinds of solution concentration and the surface morphology of silicon wafer under reaction time were mainly studied. Scanning electron microscope (SEM) and optical microscope (OM) were used to characterize it. The results showed that two different structures of nanoscale and hole shape were obtained by different solution concentration and reaction time.
Secondly, the Ag particles in the two step method and one step method of black silicon are characterized by the SEM, EDX and particle size analysis software. The results show that the two step method consumes very little heavy metals, and the distribution of metal particles is very uniform and the size of the particles has a certain regularity. Because the two step method consumes little Ag, and the follow-up can be completely residual. The metal particles are removed cleanly, avoiding the complex of the metal surface of the battery sheet.
Finally, from the structural point of view, the two step black silicon is equivalent to a nano structure on the basis of the original micron structure, that is, a micro nano composite structure is formed, which makes the reflectivity of the silicon wafer lower from about 25% to about 5% or even lower. The standard 8 degree cashmere area fractional reflectometer (D8 reflector) is used for black. The optical properties of silicon have been characterized, and it is found that it does get very low reflectivity. However, this extremely low reflectivity of black silicon has a very deep structure, that is, a large specific surface area, greatly increasing the number of surface carrier complex centers, resulting in a decrease in the conversion efficiency of the battery sheet. The depth of the nanometer trapping structure can be controlled in the ideal range by the step stripping correction. In this paper, the flow sheet analysis of the two step polycrystalline black silicon battery in Suzhou ATS sunshine Electric Technology Co., Ltd. was carried out. The flow sheet data showed that the average efficiency of the battery was 18.05%, higher than the average of the production line 17.52%.
To sum up, we have confirmed the feasibility of preparing black silicon solar cells by full liquid two step metal assisted chemical etching in the laboratory and production line, and compared with one step method. The research content of this paper can greatly promote the development of China's photovoltaic industry and the full liquid phase two step black silicon technology. There is a great potential for practical application.
【學(xué)位授予單位】：蘇州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM914.4

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