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The Status of Research on Disilane in Silane Gas Mixtures in Thin Film Silicon Solar Cells

The Status of Research on Disilane in Silane Gas Mixtures in Thin Film Silicon Solar Cells
The Status of Research on Disilane in Silane Gas Mixtures in Thin Film Silicon Solar Cells

THE STATUS OF RESEARCH ON DISILANE IN SILANE GAS MIXTURES IN THIN FILM SILICON

SOLAR CELLS

S. Gruss1, S. Petri1, H. Stiebig1, P. Szych2, J-C Cigal2, A.M. Athalye3

1 Malibu GmbH & Co. KG, Boettcherstrasse 7, D-33609 Bielefeld, Germany, sgruss@https://www.doczj.com/doc/3a18605228.html,

2Linde AG, Linde Gases Division, Seitnerstrasse 70, D-82049 Pullach, Germany, pawel.szych@https://www.doczj.com/doc/3a18605228.html, 3Linde LLC., 1970 Diamond Street, San Marcos, CA 92078, USA, atul.athalye@https://www.doczj.com/doc/3a18605228.html,

ABSTRACT: Previous work on laboratory scale has shown that a small addition of disilane in highly diluted monosilane in hydrogen can increase the film growth rate during μc-Si:H thin-film PECVD. In this work the effect of disilane on deposition rate was investigated on an industrial production-scale platform, an AKT Gen 5 tool. Both a-Si:H and μc-Si:H thin films were deposited with disilane mixtures under different process conditions and their thickness and uniformity, microstructure factor and crystallinity were measured. These thin films were integrated into solar cells in order to investigate the influence of disilane on solar cell performance. Complete solar cells were produced and their electrical parameters and light-induced degradation were measured and compared to the reference solar cells deposited under standard process conditions with pure monosilane diluted in hydrogen.

Keywords: disilane, throughput, a-Si/μc-Si, Deposition, PECVD, R&D and Demonstration Programmes, Tandem, Thin Film Solar Cell

1 INTRODUCTION

Disilane-in-silane gas mixtures were studied in the literature [1 – 6] and it was reported that a small addition of disilane (0.6% - 6.0%) to highly diluted monosilane in hydrogen can increase thin-film growth rate many-fold during μc-Si:H thin film PECVD [1]. The dissociation energy of disilane (Si-Si 76.7 kcal/mol) is lower than that of silane (Si-H 91.8 kcal/mol), so the dissociation rate of disilane in a plasma is higher which increases the electron and ion density in the plasma, leading to better silane dissociation and better gas utilization in general. The previously described experiments were performed on a laboratory scale only, while our research focused on increasing the throughput in an industrial environment as part of an overall program to find commercially relevant solutions for cost-effective manufacturing of thin-film solar cells. Therefore extensive studies on disilane additives were performed at Malibu’s R&D Centre in Bielefeld (Germany) under a Joint Development Program between Malibu GmbH & Co. KG and Linde AG. The purpose of the studies was to investigate the influence of disilane additive as a growth rate accelerant during thin film silicon solar cell deposition and its impact on the solar cell performance. Increasing the growth rate of amorphous and microcrystalline thin films would result in increased throughput of thin film silicon solar cell fabs and significantly contribute to the reduction of cost/W p.

2 EXPERIMENTAL

All the experimental work was performed at Malibu R&D Centre on an industrial AKT Gen 5 PECVD tool. Glass panels of 1100 x 1300 x 3 mm3 coated with SnO2 were used as substrate material. PECVD parameters defining a process window, like gas flows and RF power, were set up on the AKT tool and varied in order to find optimum process conditions. The plasma excitation frequency was fixed at 13.56 MHz during all the depositions.

Special gas cylinders containing a mixture of 10% Si2H6 in SiH4 were used as disilane source in all the experiments presented in this paper.

a-Si:H and μc-Si:H thin films deposited on glass were analysed at the Malibu R&D Centre by the means of Raman spectroscopy to measure crystallinity factor, by FTIR spectroscopy to measure microstructure factor and by reflectometry to measure thin film thickness and uniformity.

Entire p-i-n single junction a-Si:H and p-i-n-p-i-n tandem junction a-Si:H/μc-Si:H thin-film solar cells deposited with disilane mixtures were analysed in order to determine their initial energy conversion efficiency (η), Fill Factor (FF), short-circuit current density (J sc), open-circuit voltage (V oc), as well as their external quantum efficiency (EQE). In order to investigate the magnitude of light-induced degradation of solar cells deposited with disilane, light soaking measurements were performed under a sun simulator under standard testing conditions (STC).

3 RESULTS AND DISCUSSION

3.1 a-Si:H thin films and single junction a-Si:H thin film solar cells deposited with 10%-disilane-in-silane mixtures In order to study the influence of 10% disilane additive on a-Si:H deposition rate, a number of intrinsic a-Si:H thin film depositions were performed in which atomic Si flow was kept constant and hydrogen dilution was varied (H2 flow changed for up to ±20%). All the a-Si:H films were deposited on glass substrates.

function of atomic Si/H ratio. H2 flow varies changing the Si/H ratio. Si flow is kept constant (10% disilane in monosilane gas mixture and pure monosilane were used).

The deposition rate as a function of atomic Si/H flow ratio for monosilane and 10% disilane in monosilane mixture is presented in Figure 1.

The highest deposition rates were obtained for the hydrogen flows decreased by 20% (highest Si/H ratio). Decreasing the hydrogen flow (increasing Si/H ratio) leads to higher deposition rates in case of 10% disilane and pure monosilane mixtures. The plot presented in Figure 1 shows that the deposition rates obtained with 10% Si 2H 6 mixtures result in a deposition rate 11 – 13% higher in reference to pure SiH 4 depositions.

Crystallinity of all the deposited a-Si:H films was measured by the means of Raman spectroscopy, but no nucleation of crystalline phase was observed and no differences were found between disilane and monosilane samples.

Microstructure Factor (μSF) of all the films was also measured and the results are presented in Figure 2.

Si/H atomic flow ratio for deposited a-Si:H thin film.

The results presented in Figure 2 show that 10% disilane mixtures produce a-Si:H films with higher μSF in comparison to pure silane. For silane deposition it is known that the higher the μSF, the lower the initial energy conversion efficiency of the solar cell and the higher the light-induced degradation effect (lower stabilized energy conversion efficiency) [7]. In order to investigate if the same phenomenon occurs with disilane deposition tests, complete a-Si:H thin film solar cells were deposited with monosilane and 10% disilane mixtures. The p-layer of all the solar cells was always deposited with pure silane. The in-layers were deposited with silane or 10% disilane with different hydrogen dilution ratios. The in-layer thickness of all deposited solar cells was always kept constant, independent from deposition rate and Si precursor. The solar cells were stored in test rig for light degradation and their electrical parameters as a function of time (light irradiation) were measured. Solar cell energy conversion efficiencies (η) as a function of light irradiation time for solar cells deposited with silane and disilane are presented in Figure 3.

Obviously, the total energy conversion efficiency loss is strongly dependent on the deposition rate and does not depend significantly on the silicon source (silane or 10% disilane mixture). So the solar cells deposited with the same deposition rate degrade in a similar way independently from the precursor. The higher the deposition rate, the higher the light-induced degradation – see figure 4.

junction solar cells deposited with pure silane and 10% disilane mixtures with different Si/H atomic flow ratio. of deposition rate for pure silane and 10% disilane in silane mixtures.

Further, the influence of plasma power on deposition rate and quality of the a-Si:H single junction solar cells deposited with monosilane and 10% disilane in monosilane mixtures was studied. It is known that lower RF power could reduce the ion bombardment of the substrate, what would reduce the defect density in the film. This would lead to a solar cell that has lower LID (higher stabilized energy conversion efficiency). A number of i-layer a-Si:H films were deposited onto glass with different settings of plasma power with pure silane and 10% disilane in silane. All other process parameters were kept constant for all the deposition tests. The results are presented in Figure 5. samples are a-Si:H i-layers deposited with pure silane and 10% disilane in silane mixture.

Again the deposition rate of the films deposited with 10% disilane in silane mixture is on average about 13% higher than the one of pure silane (compare Figure 1).

Crystallinity of all the deposited a-Si:H films was measured by means of Raman spectroscopy. All the samples were amorphous – no nucleation of crystalline phase was found and there were no differences between disilane and monosilane films.

Microstructure factors of all the films were obtained. The results are presented in Figure 6.

a-Si:H film (intrinsic) as a function of RF power.

The higher the RF power (deposition rate) the higher the μSF for pure silane and 10% disilane in silane mixture. That means the lower the RF power the better the quality of the deposited film.

Surface topography of as-deposited a-Si:H thin films was measured by the means of reflectometry.

film deposited with pure silane. film deposited with 10%-disilane-in-silane gas mixture.

The results are presented in Figure 7 (films deposited with pure silane) and in Figure 8 (film deposited with a 10%-disialne-in-silane mixture). The surface of reference silane sample is clearly concave and that of the 10%-disilane-in-silane mixture is convex. Despite this difference, the non-uniformity of both films is very comparable: 0.031 for film deposited with silane, 0.039 for film deposited with the 10% disilane mixture.

Since the non-uniformity of all deposited films (both with silane and 10% disilane) was acceptable, no further optimization was performed. Nevertheless the different profiles indicate different decomposition behaviour of silane and disilane, as expected based on their different dissociation energies.

A complete p-i-n a-Si:H solar cell was deposited with the 10%-disilane-in-silane gas mixture using a reduced RF power of 351 W. Such process conditions enable deposition of a solar cell with a standard deposition rate (like the reference deposition with pure silane using 400 W of RF power). The standard deposition rate does not deteriorate the μSF and the lower RF power should decrease the ion bombardment of the grown film resulting in an improved film quality. The deposited solar cell with RF power of 351 W and 10% disilane gas mixture was degraded under a sun simulator. LID results of a reference solar cell (pure silane, 400 W) and the 10% disilane cell deposited with 351 W are given in Figure 9. junction a-Si:H solar cells. A reference a-Si:H solar cell deposited with pure silane at 400 W is compared to a cell deposited with 10%-disilane-in-silane mixture at 351 W. Deposition rate was the same for both solar cells.

The 10%-disilane-in-silane solar cell degrades similar to the reference solar cell, so decreasing the RF power to 351 W does not reduce the ion bombardment in that way that the LID effect is decreased, too.

3.2 μc-Si:H thin films and tandem a-Si:H/μc-Si:H thin film solar cells deposited with 10% disilane in silane gas mixture – preliminary results

A number of intrinsic μc-Si:H thin films were deposited with pure silane and 10%-disilane-in-silane mixture. The films were deposited onto glass substrates with constant atomic silicon flow, but different hydrogen dilution (H 2 flow varied). We present here the preliminary results of these experiments, where Si/H atomic flow ratios were kept constant.

Figure 10 shows the IV characteristics of tandem solar cells where bottom μc-Si:H cell was deposited with 10% disilane in silane mixture and pure silane.

-0,15

0,050,250,450,650,851,051,251,45

voltage [V]

c u r r e n t [m A ]

Figure 10: IV characteristics of tandem a-Si:H/μc-Si:H solar cells where bottom μc-Si:H cell was deposited with 10%-disilane-in-silane mixture and pure silane.

The IV characteristics are very similar showing no significant influence of disilane.

The external quantum efficiency (EQE) of the investigated cells was measured and the results are presented in Figure 11.

300

40050060070080090010001100

wave length [nm]

E Q E [%]

Figure 11: External quantum efficiency (EQE) of tandem a-Si:H/μc-Si:H solar cells; bottom μc-Si:H cells deposited with pure silane and 10% disilane in silane mixture

The EQE of both cells is very comparable showing no significant influence of disilane mixture.

The tandem a-Si:H/μc-Si:H solar cells were deposited with disilane in order to check if disilane-based deposition would improve film structure and lead to lower LID effect. Tandem a-Si:H/μc-Si:H solar cells were deposited: 1. reference tandem solar cell deposited with monosilane, 2. tandem solar cell deposited with 10% disilane (μc-Si:H bottom cell only, top a-Si:H cell deposited with monosilane). Although the LID effect on μc-Si:H films is not as pronounced as on a-Si:H films, the tandem solar cells were degraded under a sun simulator under standard testing condition. The results of the light soaking experiment are presented in Figure 12.

As expected, disilane mixture does not have any significant impact on the LID of the whole tandem solar cell. LID is driven by top a-Si:H cell and the contribution of μc-Si:H cell is not significant.

0,11101001000

time [h]

s o l a r c e l l e f f i c i e n c y (n o r m a l i z e d )

Figure 12: Light-induced degradation (LID) of tandem a-Si:H/μc-Si:H solar cells. Bottom μc-Si:H solar cells were deposited with monosilane (reference), 10% disilane in monosilane.

4 CONCLUSIONS

Under the applied deposition conditions on the AKT Gen 5 tool the experiments show that the addition of 10% disilane can improve the deposition rate by 11 – 13% in case of both types of experiments (hydrogen flow and RF power variations), but stabilised efficiencies decreased significantly. An increase of the deposition rate of the same magnitude could be obtained by varying the Si/H ratio also leading to a reduced stabilised energy conversion efficiency of the same order.

The standard deposition rate could be maintained under reduced RF power by using 10% disilane in silane mixture. But this did not result in any improvement of the quality of the deposited film (no improvement of the light induced degradation behaviour). Under the investigated conditions the stabilised energy conversion efficiency is primarily dependant on the rate of Si deposition and not on the precursor (SiH 4 or Si 2H 6) itself. Obviously in the investigated deposition regime there is no significant difference in the ion bombardment leading to improved film qualities and therefore reduced degradation.

The light-induced degradation depends primarily on deposition conditions (Si/H ratio or RF power) and not on Si source (silane or disilane).

Preliminary results on tandem solar cells show that μc-Si:H bottom cells deposited with disilane were very similar to the reference tandem solar cells deposited with pure monosilane giving identical external quantum efficiency and exhibiting comparable light induced degradation.

5 REFERENCES [1] A. Hammad, E. Anabatidesm D. Mataras, D.

Rapakoulias, PECVD of hydrogenated silicon thin films from SiH4+H2+Si2H6 mixtures, Thin Solid Films 451-452 (2004) 255-258

[2] H. Chatam, P. Bhat, A. Benson, C. matovich; High-efficiency amorphous silicon p-i-n solar cells deposited from disilane at rates up to 2 nm/s using VHF discharges; Journal of Non-Crystalline Solids, 115 (1989) 201 – 203

[3] W. Futako, T. Takagi, T. Nishimoto, M. Kondo, I.

Shimizu, A. Matsuda; Gas Phase Diagnosis of Disiliane/Hydrogen RF Glow Discharge Plasma and its Application to High Rate Growth of High Quality

Amorphous Silicon; Jpn. J. Appl. Phys. Vol. 38 (1999) pp. 4535 – 4537, Part 1, No. 7B, July 1999 [4] R.J. Bogaert, T.W.F. Russel, M.T. Klein, R.E.

Rocheleau, B.N. Baron; Chemical Vapour Deposition of Hydrogenated Amorphous Silicon from Disilane;

J. Electrochem. Soc. Vol. 136, No. 10, Oct. 1989 [5] P. Templer-Boyer, E. Scheid, G. Faugere, B. Rousset;

Residual stress in silicon films deposited by LPCVD from disilane; Thin Solid Films 310 (1997) 234 – 237 [6] A. Matsuda, T. Kaga, H. Tanaka, L. Malhotra, K.

Tanaka; Glow-discharge deposition of a-Si:H from pure Si2H6 and pure SiH4; Japanese Journal of Applied Physics, Vol. 22, No. 2, Feb 1983, pp.

L115 – L117

[7] A. Shah; Thin-Film Silicon Solar Cells; CRC Press,

2010 First edition, page 34 - 35

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●I wonder if it’s because I have been at school for so long that I’ve grown so crazy about going home. ●It is because she wasn’t well that she fell far behind her classmates this semester. ●I can well remember that there was a time when I took it for granted that friends should do everything for me. ●In order to make a difference to society, they spent almost all of their spare time in raising money for the charity. ●It’s no pleasure eating at school any longer because the food is not so tasty as that at home. ●He happened to be hit by a new idea when he was walking along the riverbank. ●I wonder if I can cope with stressful situations in life independently. ●It is because I take things for granted that I make so many mistakes. ●The treasure is so rare that a growing number of people are looking for it. ●He picks on the weak mn in order that we may pay attention to him. ●It’s no pleasure being disturbed whena I settle down to my work. ●I can well remember that when I was a child, I always made mistakes on purpose for fun. ●It’s no pleasure accompany her hanging out on the street on such a rainy day. ●I can well remember that there was a time when I threw my whole self into study in order to live up to my parents’ expectation and enter my dream university. ●I can well remember that she stuck with me all the time and helped me regain my confidence during my tough time five years ago. ●It is because he makes it a priority to study that he always gets good grades. ●I wonder if we should abandon this idea because there is no point in doing so. ●I wonder if it was because I ate ice-cream that I had an upset student this morning. ●It is because she refused to die that she became incredibly successful. ●She is so considerate that many of us turn to her for comfort. ●I can well remember that once I underestimated the power of words and hurt my friend. ●He works extremely hard in order to live up to his expectations. ●I happened to see a butterfly settle on the beautiful flower. ●It’s no pleasure making fun of others. ●It was the first time in the new semester that I had burned the midnight oil to study. ●It’s no pleasure taking everything into account when you long to have the relaxing life. ●I wonder if it was because he abandoned himself to despair that he was killed in a car accident when he was driving. ●Jack is always picking on younger children in order to show off his power. ●It is because he always burns the midnight oil that he oversleeps sometimes. ●I happened to find some pictures to do with my grandfather when I was going through the drawer. ●It was because I didn’t dare look at the failure face to face that I failed again. ●I tell my friend that failure is not scary in order that she can rebound from failure. ●I throw my whole self to study in order to pass the final exam. ●It was the first time that I had made a speech in public and enjoyed the thunder of applause. ●Alice happened to be on the street when a UFO landed right in front of her. ●It was the first time that I had kept myself open and talked sincerely with my parents. ●It was a beautiful sunny day. The weather was so comfortable that I settled myself into the

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英语句子结构和造句

高中英语~词性~句子成分~语法构成 第一章节:英语句子中的词性 1.名词:n. 名词是指事物的名称,在句子中主要作主语.宾语.表语.同位语。 2.形容词;adj. 形容词是指对名词进行修饰~限定~描述~的成份,主要作定语.表语.。形容词在汉语中是(的).其标志是: ous. Al .ful .ive。. 3.动词:vt. 动词是指主语发出的一个动作,一般用来作谓语。 4.副词:adv. 副词是指表示动作发生的地点. 时间. 条件. 方式. 原因. 目的. 结果.伴随让步. 一般用来修饰动词. 形容词。副词在汉语中是(地).其标志是:ly。 5.代词:pron. 代词是指用来代替名词的词,名词所能担任的作用,代词也同样.代词主要用来作主语. 宾语. 表语. 同位语。 6.介词:prep.介词是指表示动词和名次关系的词,例如:in on at of about with for to。其特征:

介词后的动词要用—ing形式。介词加代词时,代词要用宾格。例如:give up her(him)这种形式是正确的,而give up she(he)这种形式是错误的。 7.冠词:冠词是指修饰名词,表名词泛指或特指。冠词有a an the 。 8.叹词:叹词表示一种语气。例如:OH. Ya 等 9.连词:连词是指连接两个并列的成分,这两个并列的成分可以是两个词也可以是两个句子。例如:and but or so 。 10.数词:数词是指表示数量关系词,一般分为基数词和序数词 第二章节:英语句子成分 主语:动作的发出者,一般放在动词前或句首。由名词. 代词. 数词. 不定时. 动名词. 或从句充当。 谓语:指主语发出来的动作,只能由动词充当,一般紧跟在主语后面。 宾语:指动作的承受着,一般由代词. 名词. 数词. 不定时. 动名词. 或从句充当. 介词后面的成分也叫介词宾语。 定语:只对名词起限定修饰的成分,一般由形容

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它的血量十分夸张,是目前最多血量的Boss!血量夸张的达到了99999!我没有开玩笑! 他会发射悲剧蘑菇炸弹!一个炸弹甚至可以造成175的血! 他还是和以前的毒菇一样会召唤增加自己护甲的蘑菇树,但,如果你不把这个当回事,你会后悔的。 更多相关资讯请关注:饥荒:联机版专题

当悲剧毒菇的所有蘑菇树都变为最大而且所有蘑菇树都存在的时候,它的护甲会夸张的上升到99%! 这简直是夸张的一个Boss,难度无法想象! 当你过了很久很久很久终于打完后,他的掉落物如下:

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。 他可以装备手上后丢在一个地方形成一个睡包菌子区域,来使这个区域的所有的生物都睡大觉!(除玩家,不知道PVP有没有效果)。 这个睡包菌子区域可以存在18~20秒。 因为他可以它可以让生物睡觉,那么它就可以在你被追杀的时候救你一命。 当生物在这个区域内睡觉使,你攻击它(例攻击兔子),那么那个生物只会短暂逃跑或短暂揍你几下,然后继续睡觉,当你看到巨鹿在搞你家?一个睡包解决,当你看到蚁狮在你不打他的时候疯狂回血?一个睡包解决,当你看到龙蝇发怒准备放大招?一个睡包解决。 总体来说,悲剧蛤蟆是一个变T ai而又强大的生物,没有充足的经验和充足的装备请不要随意接近。 更多相关资讯请关注:饥荒:联机版专题

六级单词解析造句记忆MNO

M A: Has the case been closed yet? B: No, the magistrate still needs to decide the outcome. magistrate n.地方行政官,地方法官,治安官 A: I am unable to read the small print in the book. B: It seems you need to magnify it. magnify vt.1.放大,扩大;2.夸大,夸张 A: That was a terrible storm. B: Indeed, but it is too early to determine the magnitude of the damage. magnitude n.1.重要性,重大;2.巨大,广大 A: A young fair maiden like you shouldn’t be single. B: That is because I am a young fair independent maiden. maiden n.少女,年轻姑娘,未婚女子 a.首次的,初次的 A: You look majestic sitting on that high chair. B: Yes, I am pretending to be the king! majestic a.雄伟的,壮丽的,庄严的,高贵的 A: Please cook me dinner now. B: Yes, your majesty, I’m at your service. majesty n.1.[M-]陛下(对帝王,王后的尊称);2.雄伟,壮丽,庄严 A: Doctor, I traveled to Africa and I think I caught malaria. B: Did you take any medicine as a precaution? malaria n.疟疾 A: I hate you! B: Why are you so full of malice? malice n.恶意,怨恨 A: I’m afraid that the test results have come back and your lump is malignant. B: That means it’s serious, doesn’t it, doctor? malignant a.1.恶性的,致命的;2.恶意的,恶毒的 A: I’m going shopping in the mall this afternoon, want to join me? B: No, thanks, I have plans already. mall n.(由许多商店组成的)购物中心 A: That child looks very unhealthy. B: Yes, he does not have enough to eat. He is suffering from malnutrition.

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base on的例句

意见应以事实为根据. 3 来自辞典例句 192. The bombers swooped ( down ) onthe air base. 轰炸机 突袭 空军基地. 来自辞典例句 193. He mounted their engines on a rubber base. 他把他们的发动机装在一个橡胶垫座上. 14 来自辞典例句 194. The column stands on a narrow base. 柱子竖立在狭窄的地基上. 14 来自辞典例句 195. When one stretched it, it looked like grey flakes on the carvas base. 你要是把它摊直, 看上去就象好一些灰色的粉片落在帆布底子上. 18 来自辞典例句 196. Economic growth and human well - being depend on the natural resource base that supports all living systems. 经济增长和人类的福利依赖于支持所有生命系统的自然资源. 12 1 来自辞典例句 197. The base was just a smudge onthe untouched hundred - mile coast of Manila Bay. 那基地只是马尼拉湾一百英里长安然无恙的海岸线上一个硝烟滚滚的污点. 6 来自辞典例句 198. You can't base an operation on the presumption that miracles are going to happen. 你不能把行动计划建筑在可能出现奇迹的假想基础上.

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这是开始界面: 一汉化游戏方法 从我这下载的游戏是英文的需要使用游戏带的mod改成中文方法如下: 1.开始界面点击Play! 会弹出一个对话框(这是Steam登录用的我们登录不上) 2.点击Play Offline(离线登录) 3.菜单页面点击Mods

英语造句大全

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