TWI392103B - Method of repairing color defects of electrodes on the solar cell substrate - Google Patents
Method of repairing color defects of electrodes on the solar cell substrate Download PDFInfo
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- TWI392103B TWI392103B TW098118692A TW98118692A TWI392103B TW I392103 B TWI392103 B TW I392103B TW 098118692 A TW098118692 A TW 098118692A TW 98118692 A TW98118692 A TW 98118692A TW I392103 B TWI392103 B TW I392103B
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本發明係關於一種修復太陽能基板電極變色瑕疵的方法，尤指一種免用化學藥劑修復太陽能基板電極變色的方法。The invention relates to a method for repairing discoloration enamel of a solar substrate electrode, in particular to a method for repairing discoloration of a solar substrate electrode without using a chemical agent.
目前太陽能電池之型式主要可分為晶體矽和非晶矽兩大類。一般來說，在晶體矽的材料中，矽原子具有高度的周期性排列，因此，晶體矽太陽能電池的光電轉換效率最高，且穩定性也比較好。對於非晶矽的太陽能電池來說，由於其製作方法通常是用電漿式化學氣相沈積法，在基板上長成非晶矽的薄膜，因此其製作方式較單晶矽和多晶矽太陽能電池簡單，生產速度也最快，但是非晶矽的太陽能電池的轉換效率較晶體矽太陽能電池為低。因此，目前市面上應用最普遍的，是以晶體矽太陽能電池為主。At present, the types of solar cells can be mainly divided into two categories: crystalline germanium and amorphous germanium. In general, in the material of the crystalline germanium, the germanium atoms have a high periodic arrangement, and therefore, the crystalline germanium solar cell has the highest photoelectric conversion efficiency and good stability. For amorphous germanium solar cells, since the fabrication method is usually a plasma-based chemical vapor deposition method, an amorphous germanium film is grown on the substrate, so that the fabrication method is simpler than that of single crystal germanium and polycrystalline germanium solar cells. The production speed is also the fastest, but the conversion efficiency of amorphous silicon solar cells is lower than that of crystalline germanium solar cells. Therefore, the most common application on the market today is based on crystalline germanium solar cells.
一般來說，單體矽的製造方式通常是以矽為原料製作形成矽晶片，作為太陽能電池之基板。接著在矽晶片上摻雜或擴散微量硼、磷等摻雜物，以於晶圓上形成p-n結構。並且在矽晶片表面形成一抗反射層，之後在矽晶片的正面和背面形成金屬電極。前述的抗反射層通常是使用氮化矽利用沉積製程而形成，而金屬電極則是使用混合銀粉末的導電性漿料，藉由網版印刷法塗佈此導電性漿料後，於燒結爐中高溫燒結而成。In general, the production method of the monomer ruthenium is generally performed by using ruthenium as a raw material to form a ruthenium wafer as a substrate of a solar cell. Then, a dopant such as boron or phosphorus is doped or diffused on the germanium wafer to form a p-n structure on the wafer. And an anti-reflection layer is formed on the surface of the germanium wafer, and then a metal electrode is formed on the front and back surfaces of the germanium wafer. The antireflection layer is usually formed by a deposition process using tantalum nitride, and the metal electrode is a conductive paste using mixed silver powder. After the conductive paste is applied by screen printing, the sintering furnace is used in the sintering furnace. Sintered at medium and high temperatures.
前述導電性漿料通常包括銀粉末、含鉛玻璃料(glass frits)、有機溶劑。使用含鉛玻璃料之目的是用來在高溫燒結時蝕穿抗反射層，使得熔融的銀可以通過抗反射層和矽晶片表面接觸，於降溫之後形成導電連結，通常蝕穿抗反射層的溫度較高，約為900℃。在高溫燒結金屬電極之後，太陽能電池製作及完成，之後，依據不同需求，可以將太陽能電池加工成為太陽能電池模組。然而，完成的太陽能電池或模組，經過長期存放後，其金屬電極可能會發生變色瑕疵，影響電池外觀，造成使用者退貨。The aforementioned conductive paste generally includes silver powder, lead frits, and an organic solvent. The purpose of using lead-containing glass frit is to etch the anti-reflective layer during high-temperature sintering, so that the molten silver can be contacted by the anti-reflective layer and the surface of the germanium wafer to form a conductive bond after cooling, usually etching through the temperature of the anti-reflective layer. Higher, about 900 ° C. After the metal electrode is sintered at a high temperature, the solar cell is fabricated and completed, and then the solar cell can be processed into a solar cell module according to different needs. However, after the long-term storage of the completed solar cell or module, the metal electrode may undergo discoloration, which may affect the appearance of the battery and cause the user to return the product.
由此可知，業界目前需要一種可以修復這種電極變色瑕疵的方法，其需具備有低成本、高產出力、無污染，而且不會影響到太陽能電池或模組的電性效能。It can be seen that the industry currently needs a method for repairing such an electrode discoloration crucible, which needs to have low cost, high productivity, no pollution, and does not affect the electrical performance of the solar cell or module.
有鑑於此，本發明係提供一種修復太陽能基板電極變色瑕疵的方法，解決上述先前技藝的問題。In view of the above, the present invention provides a method of repairing a color change enthalpy of a solar substrate electrode, solving the problems of the prior art described above.
根據本發明之較佳實施例，本發明提供一種修復太陽能基板電極變色瑕疵的方法，包含：提供一太陽能基板，其中在該太陽能基板的第一表面上設有至少一表面電極，該表面電極包含一第一金屬氧化物，且該第一金屬氧化物造成該電極變色瑕疵；以及進行一低溫回火製程，將該表面電極內的該第一金屬氧化物轉變為一第二金屬氧化物，藉以修復該電極變色瑕疵。According to a preferred embodiment of the present invention, the present invention provides a method for repairing a solar substrate electrode discoloration crucible, comprising: providing a solar substrate, wherein at least one surface electrode is disposed on a first surface of the solar substrate, the surface electrode comprising a first metal oxide, and the first metal oxide causes the electrode to change color; and performing a low temperature tempering process to convert the first metal oxide in the surface electrode into a second metal oxide, thereby Repair the electrode discoloration 瑕疵.
本發明之特徵在於利用進行高溫燒結的加熱爐管來進行一低溫回火製程，藉以修復表面電極原本的顏色。此外，本發明不需使用化學藥劑便可修復電極的顏色，兼具了避免環境汙染和節省成本的優點。The present invention is characterized in that a low temperature tempering process is performed by using a heating furnace tube which performs high temperature sintering, thereby repairing the original color of the surface electrode. In addition, the invention can repair the color of the electrode without using a chemical agent, and has the advantages of avoiding environmental pollution and saving cost.
為了使 貴審查委員能更進一步了解本發明之特徵及技術內容，請參閱以下有關本發明之詳細說明與附圖。然而所附圖式僅供參考與輔助說明用，並非用來對本發明加以限制者。In order to provide a more detailed understanding of the features and technical aspects of the present invention, the following detailed description of the invention and the accompanying drawings. However, the drawings are for reference only and are not intended to limit the invention.
第1圖是根據本發明之較佳實施例所繪示的是晶矽型太陽能電池之部分結構立體圖。如第1圖所示，一太陽能電池10，包含一太陽能基板12，經過摻雜與擴散製程之後，於太陽能基板12中形成一p-n結構14，太陽能電池10另包含有一抗反射膜16設於太陽能基板12之第一表面18上、一表面電極20設於抗反射膜16上以及一背面電極22設於相對於太陽能電池10的第一表面18之一第二表面24上。通常，表面電極20所在的第一表面18是太陽能電池10的受光面，而第二表面24是太陽能電池10的背光面。1 is a perspective view showing a partial structure of a wafer type solar cell according to a preferred embodiment of the present invention. As shown in FIG. 1, a solar cell 10 includes a solar substrate 12. After the doping and diffusion process, a pn structure 14 is formed in the solar substrate 12. The solar cell 10 further includes an anti-reflection film 16 disposed on the solar cell. On the first surface 18 of the substrate 12, a surface electrode 20 is disposed on the anti-reflection film 16 and a back electrode 22 is disposed on a second surface 24 of the first surface 18 of the solar cell 10. Generally, the first surface 18 on which the surface electrode 20 is located is the light receiving surface of the solar cell 10, and the second surface 24 is the backlight surface of the solar cell 10.
一般來說，太陽能基板12可以採用單結晶或多結晶的矽基板，其中，抗反射膜16通常可以是由氮化矽所構成，但不限於此。表面電極20包含由銀、銅、鋁、鍚、銦或其它的導電材料。背面電極22較佳係由銀及鋁所構成。表面電極20和背面電極22可以利用濺鍍法、真空沉積法、網版印刷法等方式形成。於本實施例中，表面電極20主要是採用混合銀粉末的導電性漿料(銀漿)，於燒結爐中，在900℃的相對高溫下燒結而成。In general, the solar substrate 12 may be a single crystal or a polycrystalline germanium substrate, wherein the antireflection film 16 may be generally composed of tantalum nitride, but is not limited thereto. The surface electrode 20 contains a conductive material made of silver, copper, aluminum, tantalum, indium or the like. The back electrode 22 is preferably made of silver and aluminum. The surface electrode 20 and the back surface electrode 22 can be formed by a sputtering method, a vacuum deposition method, a screen printing method, or the like. In the present embodiment, the surface electrode 20 is mainly formed by sintering a conductive paste (silver paste) mixed with silver powder in a sintering furnace at a relatively high temperature of 900 °C.
為了在燒結表面電極20使得銀漿可以穿透抗反射膜16和p-n結構14電連結，通常會在銀漿中加入含鉛玻璃料，其中鉛玻璃料包含了氧化鉛(PbO)，即使在太陽能電池10完成之後，表面電極20中依然含有氧化鉛。但是，發明人發現，太陽能電池10經過長期存放後，存在於表面電極20中的氧化鉛，會氧化成高價鉛金屬氧化物，例如：PbO2 、Pb3 O4 、Pb12 O19 、Pb12 O17 和Pbx Oy ，其中x>0，y≧2，上文所述的高價鉛金屬氧化物係指包含四價鉛的金屬氧化物。由於表面電極20中的氧化鉛的顏色為黃色，經由氧化之後所形成的高價鉛金屬氧化物包含有紅色和黑色，所以，顏色較深的高價鉛金屬氧化物會造成表面電極20產生電極變色瑕疵，例如，造成表面電極20的顏色變深，影響到太陽能電池的外觀。In order to electrically bond the surface electrode 20 so that the silver paste can penetrate the anti-reflection film 16 and the pn structure 14, a lead-containing glass frit is usually added to the silver paste, wherein the lead frit contains lead oxide (PbO) even in solar energy. After the battery 10 is completed, the surface electrode 20 still contains lead oxide. However, the inventors have found that after long-term storage of the solar cell 10, the lead oxide present in the surface electrode 20 is oxidized to a high-priced lead metal oxide such as PbO 2 , Pb 3 O 4 , Pb 12 O 19 , Pb 12 . O 17 and Pb x O y , wherein x > 0, y ≧ 2, the above-mentioned high-priced lead metal oxide means a metal oxide containing tetravalent lead. Since the color of the lead oxide in the surface electrode 20 is yellow, the high-priced lead metal oxide formed after the oxidation contains red and black, so that the deep-colored high-valent lead metal oxide causes the surface electrode 20 to cause electrode discoloration. For example, the color of the surface electrode 20 is made dark, which affects the appearance of the solar cell.
因此，發明人經過長期研究，發現了一種修復太陽能基板電極變色瑕疵的方法，請參閱第2圖，第2圖繪示的是修復太陽能基板電極變色之製程示意圖，為求圖示簡單明瞭，第2圖中的太陽能電池10僅標示表面電極20。首先，提供一加熱爐管50，包含一加熱區52和一輸送帶54。接著，將表面電極20已產生電極變色瑕疵的太陽能電池10放入輸送帶54，並送入加熱區52進行一低溫回火製程。第2圖中，表面電極20上的點狀表示電極的變色瑕疵。根據本發明之一較佳實施例，所使用之加熱爐管50可以為，例如Centrotherm photovotaics所生產之設備，型號可以為DO-FF-8.600-300，加熱爐管50的加熱區52中可依序分為第1區至第6區，其中第1區至第6區可個別設定加熱溫度，太陽能電池10將由輸送帶54傳送，依序經過第1區至第6區加熱回火。根據本發明之較佳實施例，修復變色瑕疵的條件如下：輸送帶54速度為6600mm/min，加熱區52由第1區至第6區的加熱溫度分別設定為400℃、400℃、400℃、450℃、580℃、580℃。需注意的是：上述第1區至第6區之加熱溫度係為加熱爐管上內建的溫度計所讀取之溫度值，為表面電極的周圍溫度(ambient temperature)，並非表面電極的表面溫度。因此，對於不同的加熱爐管，即使最終會使表面電極的表面達到相同溫度，但依據其內建的溫度計和太陽能電池的相對位置的不同，在加熱區的溫度設定，會有不同的設定值。依據發明人量測，事實上，表面電極的表面溫度係高於605℃。除此之外，表面電極20的變色瑕疵，主要是在第5區和第6區加熱時修復。第1區至第4區的加熱可以選擇性的進行。Therefore, after long-term research, the inventors discovered a method for repairing the color-changing enamel of the solar substrate electrode. Please refer to FIG. 2, and FIG. 2 is a schematic diagram of a process for repairing the discoloration of the solar substrate electrode, which is simple and clear for the sake of illustration. The solar cell 10 in the figure 2 only indicates the surface electrode 20. First, a heating furnace tube 50 is provided which includes a heating zone 52 and a conveyor belt 54. Next, the solar cell 10 in which the surface electrode 20 has generated the electrode discoloration enamel is placed in the conveyor belt 54 and sent to the heating zone 52 for a low temperature tempering process. In Fig. 2, the dot on the surface electrode 20 indicates the discoloration enthalpy of the electrode. According to a preferred embodiment of the present invention, the heating furnace tube 50 used may be, for example, a device manufactured by Centrotherm photovotaics, the model number may be DO-FF-8.600-300, and the heating zone 52 of the heating furnace tube 50 may be The sequence is divided into the first zone to the sixth zone, wherein the heating temperature is individually set in the first zone to the sixth zone, and the solar cell 10 is transported by the conveyor belt 54 and sequentially heated and tempered through the first zone to the sixth zone. According to a preferred embodiment of the present invention, the condition for repairing the color change enthalpy is as follows: the speed of the conveyor belt 54 is 6600 mm/min, and the heating temperatures of the heating zone 52 from the first zone to the sixth zone are set to 400 ° C, 400 ° C, and 400 ° C, respectively. , 450 ° C, 580 ° C, 580 ° C. It should be noted that the heating temperature of the first zone to the sixth zone is the temperature value read by the built-in thermometer on the heating furnace tube, which is the ambient temperature of the surface electrode, not the surface temperature of the surface electrode. . Therefore, for different heating furnace tubes, even if the surface of the surface electrode is finally brought to the same temperature, depending on the relative position of the built-in thermometer and solar cell, the temperature setting in the heating zone will have different set values. . According to the inventors' measurements, in fact, the surface temperature of the surface electrode is higher than 605 °C. In addition to this, the discoloration enthalpy of the surface electrode 20 is mainly repaired when the fifth and sixth regions are heated. The heating of the first zone to the fourth zone can be selectively performed.
根據發明之另一較佳實施例，所使用之加熱爐管50同樣為Centrotherm photovotaics所生產之設備，型號為DO-FF-8.600-300，輸送帶54速度為7500mm/min，加熱區52由第1區至第6區的加熱溫度分別設定為400℃、400℃、400℃、450℃、600℃、600℃。如同前述，此處所提供的加熱溫度係亦為加熱爐管上內建的溫度計所讀取之溫度值，為表面電極的周圍溫度(ambient temperature)，並非表面電極的表面溫度。依據發明人量測，表面電極的表面溫度高於605℃。According to another preferred embodiment of the invention, the heating furnace tube 50 used is also a device produced by Centrotherm photovotaics, model DO-FF-8.600-300, conveyor belt 54 speed 7500 mm/min, heating zone 52 by The heating temperatures in the first to sixth zones were set to 400 ° C, 400 ° C, 400 ° C, 450 ° C, 600 ° C, and 600 ° C, respectively. As mentioned above, the heating temperature provided herein is also the temperature value read by the built-in thermometer on the heating furnace tube, which is the ambient temperature of the surface electrode, not the surface temperature of the surface electrode. According to the inventors' measurement, the surface temperature of the surface electrode was higher than 605 °C.
經過低溫回火製程後，高價鉛金屬氧化物會因為在605℃以上的溫度加熱，而還原為氧化鉛，使得表面電極20的電極變色瑕疵被快速修復。如第2圖所示，離開加熱區52後的太陽能電池10，其表面電極20上的變色瑕疵(第2圖中以點狀表示)消失。前述的加熱爐管50，原本之用途係為燒結爐，用於表面電極20形成時的高溫燒結製程，因此，本發明的低溫回火修復電極變色的製程和高溫燒結電極的製程，可以使用相同的加熱爐管，不需另外添購硬體。After the low-temperature tempering process, the high-priced lead metal oxide is reduced to lead oxide by heating at a temperature of 605 ° C or higher, so that the electrode discoloration of the surface electrode 20 is quickly repaired. As shown in Fig. 2, in the solar cell 10 which has left the heating zone 52, the discoloration 瑕疵 on the surface electrode 20 (indicated in dots in Fig. 2) disappears. The foregoing heating furnace tube 50 is originally used as a sintering furnace for the high-temperature sintering process when the surface electrode 20 is formed. Therefore, the process of discoloration of the low-temperature tempering repair electrode of the present invention and the process of the high-temperature sintered electrode can be the same. The heating tube does not require additional hardware.
當然，本發明修復太陽能基板電極變色瑕疵的方法，不只限於使用前述的爐管法，亦可以使用其它的加熱方式，例如，紅外線、雷射加熱方式或其它低溫回火製程，將太陽能電池的表面電極之表面溫度加熱至605℃至650℃之間，並且在表面溫度為605℃至650℃之間時，持續定溫加熱2秒至3秒，較佳者為2秒至2.9秒，才有修復電極變色瑕疵的效果。值得注意的是：若加熱的溫度太低，或時間過短，會使得表面電極之表面溫度太低，造成變色瑕疵無法修復，若加熱的溫度的溫度太高，或是加熱時間過長，則會使得表面電極之表面溫度太高，因而造成表面電極剝落，或者影響到電池電性效能。因此，加熱的溫度和時間是電極變色瑕疵修復的關鍵。Of course, the method for repairing the discoloration enamel of the solar substrate electrode of the present invention is not limited to the use of the above-mentioned furnace tube method, and other heating methods such as infrared rays, laser heating methods or other low temperature tempering processes may be used to surface the solar cell. The surface temperature of the electrode is heated to between 605 ° C and 650 ° C, and when the surface temperature is between 605 ° C and 650 ° C, the heating is continued for 2 seconds to 3 seconds, preferably 2 seconds to 2.9 seconds. Fix the effect of electrode discoloration. It is worth noting that if the heating temperature is too low, or the time is too short, the surface temperature of the surface electrode is too low, and the discoloration enamel cannot be repaired. If the temperature of the heating temperature is too high, or the heating time is too long, then The surface temperature of the surface electrode is too high, which causes the surface electrode to peel off or affect the battery electrical performance. Therefore, the temperature and time of heating are the key to the repair of the electrode discoloration.
本發明利用低溫回火的方式將太陽能基板上的表面電極之中的高價鉛金屬氧化物還原成氧化鉛，使得原本由高價鉛金屬氧化物所造成的變色瑕疵恢復，此方式不需使用化學藥劑即可除去高價鉛金屬氧化物，可避免環境汙染問題。The invention reduces the high-priced lead metal oxide among the surface electrodes on the solar substrate to lead oxide by low-temperature tempering, so that the discoloration 原 originally caused by the high-priced lead metal oxide is recovered, and the chemical agent is not needed in this way. High-priced lead metal oxides can be removed to avoid environmental pollution problems.
以上所述僅為本發明之較佳實施例，凡依本發明申請專利範圍所做之均等變化與修飾，皆應屬本發明之涵蓋範圍。The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should be within the scope of the present invention.
10．．．太陽能電池10. . . Solar battery
12．．．太陽能基板12. . . Solar substrate
14．．．p-n結構14. . . P-n structure
16．．．抗反射膜16. . . Anti-reflection film
18．．．第一表面18. . . First surface
20．．．表面電極20. . . Surface electrode
22．．．背面電極twenty two. . . Back electrode
24．．．第二表面twenty four. . . Second surface
50．．．加熱爐管50. . . Heating furnace tube
52．．．加熱區52. . . Heating zone
54．．．輸送帶54. . . conveyor
第1圖是根據本發明之較佳實施例所繪示的是晶矽型太陽能電池之立體圖。1 is a perspective view of a wafer type solar cell according to a preferred embodiment of the present invention.
第2圖繪示的是修復太陽能基板電極變色之製程示意圖。Figure 2 is a schematic diagram showing the process of repairing the discoloration of the solar substrate electrode.
10．．．太陽能電池10. . . Solar battery
20．．．表面電極20. . . Surface electrode
50．．．加熱爐管50. . . Heating furnace tube
52．．．加熱區52. . . Heating zone
54．．．輸送帶54. . . conveyor
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW098118692A TWI392103B (en) | 2009-06-05 | 2009-06-05 | Method of repairing color defects of electrodes on the solar cell substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW098118692A TWI392103B (en) | 2009-06-05 | 2009-06-05 | Method of repairing color defects of electrodes on the solar cell substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201044620A TW201044620A (en) | 2010-12-16 |
| TWI392103B true TWI392103B (en) | 2013-04-01 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW098118692A TWI392103B (en) | 2009-06-05 | 2009-06-05 | Method of repairing color defects of electrodes on the solar cell substrate |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI392103B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449885A (en) * | 2016-11-18 | 2017-02-22 | 江苏东昇光伏科技有限公司 | Photovoltaic imbrication assembly repair device and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302017A (en) * | 1998-04-22 | 1999-11-02 | Central Glass Co Ltd | Transparent electrically conductive film |
| JP2004273886A (en) * | 2003-03-11 | 2004-09-30 | Hitachi Cable Ltd | Crystalline thin film semiconductor device and photovoltaic device |
| JP2005116906A (en) * | 2003-10-10 | 2005-04-28 | Hitachi Ltd | Silicon solar battery cell and its manufacturing method |
-
2009
- 2009-06-05 TW TW098118692A patent/TWI392103B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302017A (en) * | 1998-04-22 | 1999-11-02 | Central Glass Co Ltd | Transparent electrically conductive film |
| JP2004273886A (en) * | 2003-03-11 | 2004-09-30 | Hitachi Cable Ltd | Crystalline thin film semiconductor device and photovoltaic device |
| JP2005116906A (en) * | 2003-10-10 | 2005-04-28 | Hitachi Ltd | Silicon solar battery cell and its manufacturing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449885A (en) * | 2016-11-18 | 2017-02-22 | 江苏东昇光伏科技有限公司 | Photovoltaic imbrication assembly repair device and method |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201044620A (en) | 2010-12-16 |
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