TWI430467B - Solar battery with an anti-reflect surface and the manufacturing method thereof - Google Patents

Solar battery with an anti-reflect surface and the manufacturing method thereof Download PDF

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TWI430467B
TWI430467B TW097114554A TW97114554A TWI430467B TW I430467 B TWI430467 B TW I430467B TW 097114554 A TW097114554 A TW 097114554A TW 97114554 A TW97114554 A TW 97114554A TW I430467 B TWI430467 B TW I430467B
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substrate
germanium
etching
tantalum nitride
film
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TW200945609A (en
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Chii Rong Yang
Shu Fang Chang
Mao Jung Huang
Hsing Shian Lee
Yuang Cherng Chiou
Rong Tsong Lee
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Univ Nat Taiwan Normal
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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具有抗反射表面的太陽電池的製造方法Method for manufacturing solar cell with anti-reflection surface

本發明係與太陽電池製作有關,尤指具有抗反射表面的太陽電池。The invention relates to the manufacture of solar cells, and more particularly to solar cells having an anti-reflective surface.

太陽能電池製作技術現在已大致完備,而為了追求更高的光電轉換效率,其中一種方法就是盡量避免光線被反射,而使表面粗糙化即為避免光線反射的其中一種方式,因此就發展出了將太陽電池的表面予以粗化的製造方法,以及具有粗糙表面的太陽電池。Solar cell fabrication technology is now almost complete, and in order to pursue higher photoelectric conversion efficiency, one of the methods is to avoid the light being reflected, and roughening the surface is one way to avoid light reflection, so it will develop A method of roughening the surface of a solar cell, and a solar cell having a rough surface.

這種傳統、典型的太陽電池的製造大致上就是在矽基板上進行粗糙化的製程,之後便是形成N型矽層,接著再上一層抗反射膜,然後再以如印刷的方式定義電極,如此太陽電池即告完成。然而,目前的在太陽電池表面(通常就是在矽基板上)所進行的粗糙化,即使是以濕式蝕刻的方式所製造者,其所達到的抗反射的效果有限,原因在於粗糙的程度不足,致使仍有大部分的光線被反射而離開太陽電池,因而造成浪費。The manufacture of such a conventional, typical solar cell is generally a process of roughening on a germanium substrate, followed by formation of an N-type germanium layer, followed by an anti-reflective film, and then defining the electrodes in a printed manner. So the solar battery is complete. However, the current roughening on the surface of a solar cell (usually on a germanium substrate), even if it is made by wet etching, has a limited anti-reflection effect due to insufficient roughness. As a result, most of the light is still reflected and leaves the solar cell, thus causing waste.

這個技術已行之有年,但是對於這個技術中關於抗反射的關鍵技術,即在矽基板表面作粗製化的動作,並無根本性的改革,也就是說習用技術的粗製化動作並不能達到高深寬比的需求,而也唯有高深寬比的表面才能夠使太陽電池具有較佳的抗反射性能。此外,太陽電池在使用時會因為陽光的照射而使其本身的溫度上升,導致輸出電壓與最大輸出功率的下降,而習用的太陽電池 卻未考慮散熱問題。因此唯有在製作太陽能電池技術上作到重大的革新,才能在大幅提昇光電轉換的效率。This technology has been in existence for a long time, but there is no fundamental reform for the key technology of anti-reflection in this technology, that is, the roughening of the surface of the crucible substrate, that is, the roughening action of the conventional technology cannot be achieved. The high aspect ratio requirement, but only the high aspect ratio surface can make the solar cell have better anti-reflection performance. In addition, when the solar cell is used, its temperature rises due to the irradiation of sunlight, resulting in a decrease in output voltage and maximum output power, while conventional solar cells are used. But did not consider the heat issue. Therefore, only by making major innovations in the production of solar cell technology can the efficiency of photoelectric conversion be greatly improved.

因此,在現行的太陽電池技術領域中,迫切的需要一種可以解決表面粗糙程度不足、以及因散熱不良而導致的功率下降等問題的技術。Therefore, in the field of current solar cell technology, there is an urgent need for a technique that can solve problems such as insufficient surface roughness and power reduction due to poor heat dissipation.

有鑑於以傳統的太陽電池的製作方法對於抗反射效能的提昇極為有限,本發明在矽基表面上作高深寬比的結構,透過高深寬比的結構來達到抗反射的效果並進而提昇光電轉換的效率。In view of the fact that the conventional solar cell manufacturing method has extremely limited improvement in anti-reflection performance, the present invention has a high aspect ratio structure on the surface of the ruthenium base, and achieves an anti-reflection effect through a high aspect ratio structure and further enhances photoelectric conversion. s efficiency.

為了達到上述之目的,本發明提供一種具有抗反射表面的太陽電池的製造方法,包括下列步驟:(1)提供一矽基板,該矽基板具有正面與背面;(2)形成一第一氮化矽層於該正面上;(3)舖設奈米球於該氮化矽層上,以奈米球為第一蝕刻遮罩;(4)以反應式離子蝕刻技術蝕刻該氮化矽層,形成蝕刻窗於該氮化矽層上;(5)移除該奈米球;(6)蝕刻該矽基板用以形成深凹型結構;以及(7)在該矽基板的該正面形成一正面電極,而在該背面形成一背面電極。In order to achieve the above object, the present invention provides a method for fabricating a solar cell having an anti-reflective surface, comprising the steps of: (1) providing a germanium substrate having a front side and a back side; and (2) forming a first nitride. a layer of germanium on the front side; (3) laying a nanosphere on the tantalum nitride layer, using a nanosphere as a first etching mask; (4) etching the tantalum nitride layer by a reactive ion etching technique to form Etching the window on the tantalum nitride layer; (5) removing the nanosphere; (6) etching the germanium substrate to form a deep concave structure; and (7) forming a front electrode on the front surface of the germanium substrate, A back electrode is formed on the back surface.

如上所述的方法,其中步驟(2)的該氮化矽層是以射頻濺鍍的方式製造。The method as described above, wherein the tantalum nitride layer of the step (2) is fabricated by means of radio frequency sputtering.

如上所述的方法,其中步驟(1)更包含一步驟(1-1):在該矽基板的正面摻雜五價元素做氮離子擴散。The method as described above, wherein the step (1) further comprises a step (1-1): doping a pentavalent element on the front side of the germanium substrate for nitrogen ion diffusion.

如上所述的方法,其中步驟(5)更包括步驟(5-1):於該矽基板的背面形成一導電層。The method as described above, wherein the step (5) further comprises the step (5-1): forming a conductive layer on the back surface of the germanium substrate.

如上所述的方法,其中步驟(5-1)的該導電層係用來作為光輔助電化學蝕刻產生電場之用。The method as described above, wherein the conductive layer of the step (5-1) is used for generating an electric field as photo-assisted electrochemical etching.

如上所述的方法,其中步驟(6)更包含一步驟(6-1):於該矽基板上形成一第二氮化矽層,並於該第二氮化矽層形成裸露處使該矽基板露出於該第二氮化矽外。The method as described above, wherein the step (6) further comprises a step (6-1): forming a second tantalum nitride layer on the germanium substrate, and forming the exposed portion on the second tantalum nitride layer to make the germanium The substrate is exposed outside the second tantalum nitride.

如上所述的方法,其中在步驟(7)之前更包括一步驟:在該矽基板背面形成一矽薄膜。The method as described above, further comprising a step of forming a tantalum film on the back surface of the tantalum substrate before the step (7).

如上所述的方法,其中步驟(7)所述的正面電極,是設於該裸露處而與該矽基板電連接。In the method as described above, the front electrode of the step (7) is disposed at the bare portion and electrically connected to the germanium substrate.

如上所述的方法,其中步驟(6)更包含下列步驟:(6-1’):於該矽基板上形成一重摻雜矽薄膜;以及(6-2’):於該重摻雜矽薄膜上形成一第二氮化矽層,並於該重摻雜矽薄膜與該第二氮化矽層上形成裸露處使該矽基板露出於該重摻雜矽薄膜與該第二氮化矽外。The method as described above, wherein the step (6) further comprises the steps of: (6-1'): forming a heavily doped germanium film on the germanium substrate; and (6-2'): the heavily doped germanium film Forming a second tantalum nitride layer thereon, and forming a bare place on the heavily doped germanium film and the second tantalum nitride layer to expose the germanium substrate to the heavily doped germanium film and the second tantalum nitride .

如上所述的方法,其中步驟(7)所述的正面電極,是位於該裸露處因而穿過該重摻雜矽薄膜與該第二氮化矽層而與該矽基板電連接。The method as described above, wherein the front electrode of the step (7) is located at the bare portion and is electrically connected to the germanium substrate through the heavily doped germanium film and the second tantalum nitride layer.

如上所述的方法,其中步驟(6)是以光輔助電化學蝕刻的方式,蝕刻該矽基板。The method as described above, wherein the step (6) etches the tantalum substrate in a photo-assisted electrochemical etching manner.

如上所述的方法,其中在步驟(6)之前,更包含一步驟:在該矽基板上預蝕出凹坑。The method as described above, wherein before the step (6), further comprising the step of pre-etching the pits on the germanium substrate.

如上所述的方法,其中該凹坑係以非等向性濕式蝕刻來製造。The method as described above, wherein the pit is fabricated by anisotropic wet etching.

為了達到上述之目的,本發明又提供一種具有抗反射表面的太陽電池的製造方法,包括下列步驟:(1)提供一矽基板,該矽基板具有正面與背面;(2)舖設奈米球於該正面上,並以該奈米球為 蝕刻遮罩;(4)蝕刻該矽基板用以形成深凹型結構;(5)移除該奈米球;以及(6)在該矽基板的該正面形成一正面電極,而在該背面形成一背面電極。In order to achieve the above object, the present invention further provides a method for manufacturing a solar cell having an anti-reflection surface, comprising the steps of: (1) providing a substrate having a front side and a back side; and (2) laying a nanosphere on the substrate. On the front side, and the nanosphere is Etching the mask; (4) etching the germanium substrate to form a deep concave structure; (5) removing the nanosphere; and (6) forming a front electrode on the front surface of the germanium substrate, and forming a front electrode on the back surface Back electrode.

如前所述的方法,其中步驟(4)是以高密度電漿反應式離子蝕刻(ICP-RIE)技術蝕刻該矽基板。The method as previously described, wherein the step (4) etches the tantalum substrate by a high density plasma reactive ion etching (ICP-RIE) technique.

如前所述的方法,其中步驟(6)更包含下列步驟:(6-a)於該矽基板上形成一第二氮化矽層;(6-b)於該第二氮化矽層形成裸露處使該矽基板露出於該第二氮化矽外;(6-c)於該矽基板的正面形成該正面電極,其中該正面電極通過該裸露處而與該矽基板電連接;(6-d)於該矽基板的背面形成一矽薄膜;以及(6-e)在該矽薄膜下形成該背面電極。The method as described above, wherein the step (6) further comprises the steps of: (6-a) forming a second tantalum nitride layer on the germanium substrate; (6-b) forming the second tantalum nitride layer Exposing the germanium substrate to the outside of the second tantalum nitride; (6-c) forming the front electrode on the front surface of the germanium substrate, wherein the front electrode is electrically connected to the germanium substrate through the bare portion; -d) forming a tantalum film on the back side of the tantalum substrate; and (6-e) forming the back surface electrode under the tantalum film.

如前所述的方法,其中該矽基板為N型矽,則該矽薄膜則為重摻雜的P型矽。In the method as described above, wherein the tantalum substrate is an N-type tantalum, the tantalum film is a heavily doped P-type tantalum.

如前所述的方法,其中該矽基板為P型矽,則該矽薄膜則為重摻雜的N型矽。In the method as described above, wherein the germanium substrate is a P-type germanium, the germanium film is a heavily doped N-type germanium.

如申請專利範圍第1項所述的方法,其中步驟(6)更包含下列步驟:(6-a’):於該矽基板上形成一重摻雜矽薄膜;(6-b’):於該重摻雜矽薄膜上形成一第二氮化矽層,並於該重摻雜矽薄膜與該第二氮化矽層上形成裸露處使該矽基板曝露於該重摻雜矽薄膜與該第二氮化矽外;(6-c’)於該矽基板的正面形成該正面電極,其中該正面電極通過該裸露處而與該矽基板電連接;以及(6-d’)於該矽基板的背面形成該背面電極。The method of claim 1, wherein the step (6) further comprises the step of: (6-a'): forming a heavily doped germanium film on the germanium substrate; (6-b'): Forming a second tantalum nitride layer on the heavily doped germanium film, and forming a bare portion on the heavily doped germanium film and the second tantalum nitride layer to expose the germanium substrate to the heavily doped germanium film and the first (6-c') forming the front electrode on a front surface of the germanium substrate, wherein the front electrode is electrically connected to the germanium substrate through the bare portion; and (6-d') the germanium substrate The back surface is formed on the back side.

如前所述的方法,其中該矽基板為N型矽,則該重摻雜矽薄膜則為P型矽。In the method as described above, wherein the germanium substrate is an N-type germanium, the heavily doped germanium film is a P-type germanium.

如前所述的方法,其中該矽基板為P型矽,則該重摻雜矽薄膜則為N型矽。In the method as described above, wherein the germanium substrate is a P-type germanium, the heavily doped germanium film is an N-type germanium.

請參見圖1至4,為本發明製造方法中,以氮化矽作為製造深凹型結構之蝕刻遮罩(蝕刻窗)的步驟示意圖。首先,請參閱圖1,其中揭示在一矽基板1上形成第一氮化矽層2。一般而言會自物理氣相沉積(PVD)或化學氣相沉積(CVD)中選擇一種作為第一氮化矽層2的形成方式。在第一氮化矽層2形成之後,便是將奈米球3設置於第一氮化矽層2上,至於設置的方法則以旋轉塗佈或是浸泡,使奈米球3附著於第一氮化矽層2上。由於是要以第一氮化矽層2作為蝕刻矽基板1的遮罩,故第一氮化矽層2本身也需要被定義出哪個部分要鏤空、哪個部分要保留,因此,奈米球3就是作為決定第一氮化矽層2成為某一種遮罩型態的另一個遮罩,可以說是一個預備遮罩,這裡則稱作第一遮罩。由於是以呈球狀的奈米球3作為遮罩,可見球與球之間的空隙即是可以被穿透的部分而成為了所謂的蝕刻窗,因此,為了避免不規則的蝕刻圖樣、即空隙有大有小,或是有空隙的上方被其他的球擋住,因此奈米球3的最佳排列是單層最密排列使球與球之間留下近似正三角形的空隙,以利蝕刻物穿過空隙抵達第一氮化矽層2。1 to 4 are schematic views showing the steps of using the tantalum nitride as an etching mask (etching window) for manufacturing a deep concave structure in the manufacturing method of the present invention. First, referring to FIG. 1, a first tantalum nitride layer 2 is formed on a germanium substrate 1. Generally, one of physical vapor deposition (PVD) or chemical vapor deposition (CVD) is selected as the formation of the first tantalum nitride layer 2. After the first tantalum nitride layer 2 is formed, the nanosphere 3 is placed on the first tantalum nitride layer 2, and the method of setting is applied by spin coating or soaking to attach the nanosphere 3 to the first layer. A layer of tantalum nitride 2 is used. Since the first tantalum nitride layer 2 is to be used as a mask for etching the germanium substrate 1, the first tantalum nitride layer 2 itself needs to be defined which portion is to be hollowed out and which portion is to be retained. Therefore, the nanosphere 3 It is another mask that determines that the first tantalum nitride layer 2 is in a certain mask type, and can be said to be a preliminary mask, which is referred to as a first mask. Since the spherical nanosphere 3 is used as a mask, it is seen that the gap between the ball and the ball is a portion that can be penetrated into a so-called etching window, and therefore, in order to avoid an irregular etching pattern, The gap is large or small, or the upper part of the gap is blocked by other balls. Therefore, the optimal arrangement of the nanosphere 3 is that the single layer is arranged in the closest order to leave a space of approximately equilateral triangle between the ball and the ball for etching. The object reaches the first tantalum nitride layer 2 through the gap.

請參見圖2,其中揭示了奈米球3間的空隙圖案已轉到第一氮化矽層2上,並在第一氮化矽層2上形成了蝕刻窗20,至此便可將奈米球3去除。Referring to FIG. 2, it is revealed that the gap pattern between the nanospheres 3 has been transferred to the first tantalum nitride layer 2, and an etching window 20 is formed on the first tantalum nitride layer 2, thereby enabling the nanometer to be used. Ball 3 is removed.

請參見圖3,其中揭示了在已去除奈米球3之後,在矽基板1的背面形成一導電層4,此導 電層4是作為一背表面電場,係用於光輔助電化學蝕刻產生電場。又,此導電層4通常透過、網印、蒸鍍、濺鍍等方式,將金、銅、鉑等金屬形成在矽基板1的背面。Referring to FIG. 3, it is disclosed that after the nanosphere 3 has been removed, a conductive layer 4 is formed on the back surface of the germanium substrate 1. The electrical layer 4 acts as a back surface electric field for photo-assisted electrochemical etching to generate an electric field. Further, the conductive layer 4 is formed by forming a metal such as gold, copper or platinum on the back surface of the ruthenium substrate 1 by means of transmission, screen printing, vapor deposition, sputtering or the like.

請參見圖4,其中揭示了以光輔助電化學蝕刻的方式,在矽基板1上蝕刻出深凹型結構10、也就是深凹孔狀、深凹槽狀的結構。一般而言,此深凹型結構10是具有高深寬比的,也就是說深度要比寬度多很多,通常,為了達到有效的抗反射的效果,其寬度要小於入射光的波長,而深度要大於入射光的波長。至此,一太陽電池的抗反射結構的部分大致上已經完成。Referring to FIG. 4, it is disclosed that a deep concave structure 10, that is, a deep concave hole shape or a deep groove shape, is etched on the ruthenium substrate 1 by photo-assisted electrochemical etching. In general, the deep-concave structure 10 has a high aspect ratio, that is, the depth is much larger than the width. Generally, in order to achieve an effective anti-reflection effect, the width is smaller than the wavelength of the incident light, and the depth is greater than The wavelength of the incident light. At this point, the portion of the anti-reflective structure of a solar cell has been substantially completed.

請參見圖5至6,為本發明製造方法中,直接以奈米球作為製造深凹型結構之蝕刻遮罩(蝕刻窗)的步驟示意圖。請先參閱圖5,其中揭示了在矽基板1上設置有奈米球3,且一如之前所述,通常是利用旋轉塗佈或是浸泡,使奈米球3附著於矽基板1上。而奈米球3較佳的排列方式是讓奈米球3以單層最密堆積的方式排列在矽基板1上。5 to 6, in the manufacturing method of the present invention, a step of directly using a nanosphere as an etching mask (etching window) for manufacturing a deep concave structure. Referring first to FIG. 5, it is disclosed that the nanosphere 3 is disposed on the ruthenium substrate 1, and as described above, the nanosphere 3 is usually attached to the ruthenium substrate 1 by spin coating or immersion. The preferred arrangement of the nanospheres 3 is such that the nanospheres 3 are arranged on the ruthenium substrate 1 in a manner that the single layer is most closely packed.

請參閱圖6,在奈米球3堆積完成後,便以奈米球3為蝕刻遮罩,透過乾式蝕刻的方式,蝕刻矽基板1,其中,在各種的乾式蝕刻方法中,通常以高密度電漿反應式離子蝕刻(ICP-RIE)技術來蝕刻矽基板1。此外,以上所述的奈米球3得以聚苯乙烯為材質。Referring to FIG. 6, after the nanosphere 3 is stacked, the nanosphere 3 is used as an etch mask, and the germanium substrate 1 is etched by dry etching. Among various dry etching methods, usually high density is used. A plasma reactive ion etching (ICP-RIE) technique is used to etch the germanium substrate 1. Further, the nanosphere 3 described above is made of polystyrene.

圖7,為本發明減薄矽基板的示意圖,其中若以圖1至圖4的實施例而言,首先要去除第一氮化矽層2以及背表面的導電層4,之後才再對 矽基板1背面全體進行蝕刻,以求減薄矽基板1的厚度。若以圖5至圖6的實施例而言,則是在移除奈米球3之後就可以對矽基板1背面全體進行蝕刻。至於圖7中用以減薄矽基板1的蝕刻液,則可以選用KOH或是TMAH;又,或是利用高密度電漿反應式離子蝕刻(ICP-RIE)技術來減薄矽基板1。7 is a schematic view of a thinned germanium substrate according to the present invention, wherein in the embodiment of FIGS. 1 to 4, the first tantalum nitride layer 2 and the conductive layer 4 on the back surface are first removed, and then The entire back surface of the substrate 1 is etched to reduce the thickness of the ruthenium substrate 1. In the embodiment of FIGS. 5 to 6, the entire back surface of the ruthenium substrate 1 can be etched after the removal of the nanosphere 3. As for the etching liquid for thinning the tantalum substrate 1 in FIG. 7, KOH or TMAH may be used; or the high-density plasma reactive ion etching (ICP-RIE) technique may be used to thin the tantalum substrate 1.

圖8至圖10,為本發明太陽電池的矽材料形成方式與上下電極配置的實施例示意圖。請先參閱圖8,為了使抗反射的效果更好,通常在矽基板1的表面上會再設置一抗反射膜,在圖8中則是以第二氮化矽層5作為抗反射膜,並且再第二氮化矽層5上更形成一裸露處50,使矽基板1可以暴露在第二氮化矽層5外。所述裸露處50是將矽基板1裸露出來的意思,一般上是在氮化矽層5上以微影蝕刻製程或是精密切割機製造出通孔、凹槽、孔穴之類的結構,使其下的材料得以裸露出來。8 to 10 are schematic views showing an embodiment of a method for forming a tantalum material and a configuration of upper and lower electrodes of a solar cell of the present invention. Referring to FIG. 8 , in order to make the anti-reflection effect better, an anti-reflection film is usually disposed on the surface of the crucible substrate 1 , and in FIG. 8 , the second tantalum nitride layer 5 is used as an anti-reflection film. And a second exposed portion 50 is further formed on the second tantalum nitride layer 5, so that the germanium substrate 1 can be exposed outside the second tantalum nitride layer 5. The exposed portion 50 is intended to expose the germanium substrate 1. Generally, a structure such as a via hole, a groove, a hole, or the like is formed on the tantalum nitride layer 5 by a micro-etching process or a precision cutting machine. The material under it can be exposed.

請接著參閱圖9,其中揭露在矽基板1的背面形成了一第一矽薄膜6,由於本發明是太陽電池,因此第一矽薄膜6與矽基板1的矽是不同型態的矽,如矽基板1是P型矽,則第一矽薄膜6就是N型矽,反之若矽基板1是N型矽,則第一矽薄膜6就是P型矽,此外,通常此第一矽薄膜6的材料是重摻雜的矽。在第一矽薄膜6成形之後,即於其上設置下電極7a。之後請參閱圖10,此時在矽基板1的正面,即氮化矽層5的裸露處50設置上電極7b,而上電極7b即穿過裸露處50與矽基板1電連接。至此,一具有抗反射結構的 太陽電池即告完成。Referring to FIG. 9, it is disclosed that a first germanium film 6 is formed on the back surface of the germanium substrate 1. Since the present invention is a solar cell, the first germanium film 6 and the germanium substrate 1 are different in shape, such as When the ruthenium substrate 1 is a P-type 矽, the first ruthenium film 6 is an N-type 矽, whereas if the ruthenium substrate 1 is an N-type 矽, the first conductive film 6 is a P-type 矽, and in addition, usually the first ruthenium film 6 The material is heavily doped ruthenium. After the first tantalum film 6 is formed, the lower electrode 7a is placed thereon. Referring to FIG. 10 at this time, the upper electrode 7b is disposed on the front surface of the germanium substrate 1, that is, the exposed portion 50 of the tantalum nitride layer 5, and the upper electrode 7b is electrically connected to the germanium substrate 1 through the bare portion 50. So far, an anti-reflective structure The solar battery is complete.

圖11至圖12,為本發明太陽電池的矽材料形成方式與上下電極配置的另一實施例示意圖。請先參閱圖11,是在矽基板1的正面設置一重摻雜的第二矽薄膜6’,其中,若矽基板1是P型矽,則第二矽薄膜6’就是N型矽,反之若矽基板1是N型矽,則第二矽薄膜6’就是P型矽,在第二矽薄膜6’形成之後,則再於其上形成一第三氮化矽層5’作為抗反射膜。為了使矽基板1裸露而出,在第三氮化矽層5’與第二矽薄膜6’上以黃光微影蝕刻或是晶圓精密切割機製造出裸露處50。11 to 12 are schematic views showing another embodiment of the formation of the tantalum material and the arrangement of the upper and lower electrodes of the solar cell of the present invention. Referring to FIG. 11, a heavily doped second germanium film 6' is disposed on the front surface of the germanium substrate 1, wherein if the germanium substrate 1 is a P-type germanium, the second germanium film 6' is an N-type germanium, and vice versa. The ruthenium substrate 1 is an N-type ruthenium, and the second ruthenium film 6' is a P-type ruthenium. After the second ruthenium film 6' is formed, a third tantalum nitride layer 5' is formed thereon as an anti-reflection film. In order to expose the germanium substrate 1, a bare place 50 is formed on the third tantalum nitride layer 5' and the second tantalum film 6' by a yellow photolithography or a wafer precision cutter.

請參閱圖12,其中在第三氮化矽層5’的裸露處50上形成一上電極7b,而上電極7b的材料穿過裸露處50抵達矽基板1並與矽基板1電連接。此外,並再矽基板1的背面形成一下電極7a。至此,一具有抗反射結構的太陽電池即告完成。Referring to Fig. 12, an upper electrode 7b is formed on the exposed portion 50 of the third tantalum nitride layer 5', and the material of the upper electrode 7b passes through the exposed portion 50 to reach the tantalum substrate 1 and is electrically connected to the tantalum substrate 1. Further, the lower electrode 7a is formed on the back surface of the substrate 1 again. At this point, a solar cell with an anti-reflective structure is completed.

此外,前述的抗反射膜亦可以多層膜的方式設置抗反射膜,通常具有兩層,一個第一層抗反射膜、一個第二層抗反射膜。其中第一層抗反射膜,其材料選自二氧化矽(SiO2 )、類鑽碳(DLC)、二氧化鈰(CcO2 )、三氧化二鋁(Al2 O3 )、以及氮化矽(Si3 N4 )中的一種;而第二層抗反射膜,其材料選自二氧化鈦(TiO)及氧化鉭(TaO5 )中的一種,且第二層所選的材料之折射率大於該第一層所選擇的材料。Further, the anti-reflection film described above may be provided with an anti-reflection film in the form of a multilayer film, and generally has two layers, a first anti-reflection film and a second anti-reflection film. The first antireflection film is selected from the group consisting of cerium oxide (SiO 2 ), diamond-like carbon (DLC), ceria (CcO 2 ), aluminum oxide (Al 2 O 3 ), and tantalum nitride. One of (Si 3 N 4 ); and the second antireflective film, the material of which is selected from one of titanium dioxide (TiO) and tantalum oxide (TaO 5 ), and the refractive index of the selected material of the second layer is greater than The material selected in the first layer.

至於上述的抗反射膜則以選自物理氣相沉積(PVD)、化學氣相沉積(CVD)、旋轉塗覆(spin-on deposition)、噴射沉積(spray deposition)與浸鍍(dip coating)中的一種方法,形成於矽基板1(請 配合圖8)或第二矽薄膜6’(請配合圖11)上。之後,更可再進行一個加熱步驟,通常比較方便的是將太陽電池送回用來形成抗反射膜的機台內。這個加熱步驟可使得位於該凸出部12邊緣的抗反射膜材料收縮,而相對的位於該凸出部12中間位置的抗反射膜材料則相對的凸起,形成有如微透鏡(micro lens)結構,而能達到聚焦的效果。As for the anti-reflection film described above, it is selected from the group consisting of physical vapor deposition (PVD), chemical vapor deposition (CVD), spin-on deposition, spray deposition, and dip coating. a method of forming on the ruthenium substrate 1 (please Cooperate with Figure 8) or the second film 6' (please match Figure 11). Thereafter, a further heating step can be performed, and it is generally convenient to return the solar cell to the machine for forming the anti-reflection film. This heating step can cause the anti-reflection film material located at the edge of the projection 12 to contract, and the opposite anti-reflection film material located at the intermediate position of the projection 12 is relatively convex, forming a micro lens structure. And can achieve the effect of focusing.

總體而言,本發明為了達到更好的抗反射效果,利用深蝕刻的方式在太陽電池的表面形成深凹形結構,使得射入的光線極不易自當中反射回大氣中,而利用的深蝕刻方式則有光輔助電化學蝕刻或是高密度電漿反應式離子蝕刻,至於蝕刻時所需要的遮罩,若以高密度電漿反應式離子蝕刻,則本發明直接以奈米化的聚苯乙烯球,簡稱奈米球來作為遮罩,當奈米球以單層最密的型態排列於矽基板上時,奈米球之間的空隙即可作為蝕刻窗,使其下方的矽基板被蝕刻,也就是說奈米球之間的孔洞圖案被轉移到矽基板上。又,若是以光輔助電化學蝕刻,則就必須以氮化矽作為蝕刻遮罩,而此氮化矽遮罩的蝕刻窗,則不同於習用技術以微影蝕刻製造,但卻是以奈米球來製造,亦即透過奈米球間的空隙作為蝕刻氮化矽的蝕刻窗,亦稱為奈米球蝕刻窗,並透過反應式離子蝕刻技術將奈米球間的孔洞圖案轉移到氮化矽層上,如此一來,氮化矽層上的蝕刻窗即是奈米球間的孔洞圖案,之後移除掉奈米球後,氮化矽層即作為使用光輔助電化學技術蝕刻矽基板時的蝕刻遮罩。此外,為了使光輔助電化學蝕刻得以順利進行,在進行之前先利用非等向性蝕刻在矽 基板上型成漸縮狀的坑,以便形成一內凹狀的尖點,而其立體結構則有如倒金字塔形。In general, in order to achieve a better anti-reflection effect, the present invention forms a deep concave structure on the surface of the solar cell by means of deep etching, so that the incident light is not easily reflected back to the atmosphere from the middle, and the deep etching is utilized. The method is photo-assisted electrochemical etching or high-density plasma reactive ion etching. As for the mask required for etching, if high-density plasma reactive ion etching, the present invention directly uses nano-sized polyphenylene. A vinyl sphere, referred to as a nanosphere, is used as a mask. When the nanospheres are arranged on the tantalum substrate in the most dense form of a single layer, the gap between the nanospheres can be used as an etching window to make the underlying germanium substrate It is etched, that is, the pattern of holes between the nanospheres is transferred to the ruthenium substrate. Moreover, in the case of photo-assisted electrochemical etching, it is necessary to use tantalum nitride as an etching mask, and the etching window of the tantalum nitride mask is different from the conventional technique by micro-etching, but it is nanometer. The ball is manufactured, that is, through the gap between the nanospheres as an etching window for etching tantalum nitride, also known as a nanosphere etching window, and transferring the hole pattern between the nanospheres to the nitriding through reactive ion etching technology. On the ruthenium layer, the etched window on the tantalum nitride layer is the hole pattern between the nanospheres. After the nanosphere is removed, the tantalum nitride layer is used as a photo-assisted electrochemical technique to etch the ruthenium substrate. Etched mask. In addition, in order to make the light-assisted electrochemical etching proceed smoothly, an anisotropic etching is used before the etching. The substrate is formed into a tapered pit to form a concave cusp, and the three-dimensional structure is like an inverted pyramid.

以球狀物來作為蝕刻遮罩的好處在於當其以最密集堆積的方式排列時,各個球體會以其自身的形狀排列出最密集的狀態,因此以球狀物而言即會排列成三顆球之間有個類似正三角形但三邊往內凹的三角狀的圖案,以此作為蝕刻遮罩,就不需要如同以往的微影蝕刻技術的光罩、感光劑、顯影藥水、曝光等等的材料與製程,因此就某種程度上而言是有其方便性的。再者,由於本發明所要製造的深凹形結構本身僅僅是作為一種粗糙表面的效果,因此並不需要複雜的圖形。此外,由於本發明所使用的是奈米化的球體,除了使深凹形結構更加密集、更加微小之外,還使得真球度提高,真球度提高即代表奈米球在最密集單層排列的時候其圖案更加的整齊劃一,可以降低那些不規則的、大小不一的蝕刻窗圖案出現的頻率降低。因此,對於要在太陽電池上製造出深凹形結構用以增加表面粗糙度以達到抗反射效果之目的,以奈米球作為製造此凹形結構的蝕刻遮罩可以說是最理想、最方便、最便宜的製造方法。The advantage of using a sphere as an etch mask is that when they are arranged in the most densely packed manner, each sphere will be arranged in its most dense state in its own shape, so that it will be arranged in three spheres. There is a triangular pattern resembling an equilateral triangle but recessed on three sides. As an etch mask, there is no need for a mask, sensitizer, developing syrup, exposure, etc. like the conventional lithography technique. Etc. Materials and processes, so to some extent it is convenient. Moreover, since the deep concave structure to be manufactured by the present invention itself is merely an effect as a rough surface, a complicated pattern is not required. In addition, since the nanosphere is used in the present invention, in addition to making the deep concave structure denser and more compact, the true sphericity is improved, and the true sphericity is increased, that is, the nanosphere is in the densest single layer. When arranged, the pattern is more uniform and uniform, which can reduce the frequency of occurrence of irregular, unequal etched window patterns. Therefore, for the purpose of manufacturing a deep concave structure on a solar cell for increasing the surface roughness to achieve an anti-reflection effect, it is most desirable and convenient to use the nanosphere as an etching mask for manufacturing the concave structure. The cheapest manufacturing method.

本發明遭熟習技術領域之人所任為匠思之修飾,皆不脫本發明申請專利範圍之保護。The invention is intended to be modified by those skilled in the art, without departing from the scope of the invention.

1‧‧‧矽基板1‧‧‧矽 substrate

10‧‧‧深凹形結構10‧‧‧Deep concave structure

2‧‧‧第一氮化矽層2‧‧‧First tantalum layer

20‧‧‧蝕刻窗20‧‧‧etching window

3‧‧‧奈米球3‧‧‧Nami Ball

4‧‧‧背表面電極4‧‧‧Back surface electrode

5‧‧‧第二氮化矽層5‧‧‧Second tantalum layer

5’‧‧‧第三氮化矽層5'‧‧‧ third tantalum layer

50‧‧‧裸露處50‧‧‧naked places

6‧‧‧蝕刻導電層6‧‧‧ Etched conductive layer

6‧‧‧第一矽薄膜6‧‧‧First film

6’‧‧‧第二矽薄膜6'‧‧‧second film

7a‧‧‧下電極7a‧‧‧ lower electrode

7b‧‧‧上電極7b‧‧‧Upper electrode

圖1至4,為本發明製造方法中,以氮化矽作為製造深凹型結構之蝕刻遮罩(蝕刻窗)的步驟示意圖;圖5至6,為本發明製造方法中,直接以奈 米球作為製造深凹型結構之蝕刻遮罩(蝕刻窗)的步驟示意圖;圖7,為本發明減薄矽基板的示意圖;圖8至圖10,為本發明太陽電池的矽材料形成方式與上下電極配置的實施例示意圖;以及圖11至圖12,為本發明太陽電池的矽材料形成方式與上下電極配置的另一實施例示意圖。1 to 4 are schematic views showing the steps of using a tantalum nitride as an etching mask (etching window) for manufacturing a deep concave structure in the manufacturing method of the present invention; and FIGS. 5 to 6, in the manufacturing method of the present invention, directly FIG. 7 is a schematic view showing a step of manufacturing an etched mask (etching window) of a deep concave structure; FIG. 7 is a schematic view showing a thinned ruthenium substrate of the present invention; and FIG. 8 to FIG. A schematic diagram of an embodiment of an electrode configuration; and FIGS. 11 to 12 are schematic views of another embodiment of a method of forming a tantalum material and an arrangement of upper and lower electrodes of a solar cell of the present invention.

1‧‧‧矽基板1‧‧‧矽 substrate

10‧‧‧深凹形結構10‧‧‧Deep concave structure

2‧‧‧第一氮化矽層2‧‧‧First tantalum layer

20‧‧‧蝕刻窗20‧‧‧etching window

3‧‧‧奈米球3‧‧‧Nami Ball

Claims (13)

一種具有抗反射表面的太陽電池的製造方法,包括下列步驟:(1)提供一矽基板,該矽基板具有正面與背面;(2)形成一第一氮化矽層於該正面上;(3)舖設奈米球於該氮化矽層上,以奈米球為第一蝕刻遮罩;(4)以反應式離子蝕刻技術蝕刻該氮化矽層,形成蝕刻窗於該氮化矽層上;(5)移除該奈米球;(6)蝕刻該矽基板用以形成深凹型結構,其中步驟(6)接著更包含下列步驟:(6-1’)於該矽基板上形成一重摻雜矽薄膜;以及(6-2’)於該重摻雜矽薄膜上形成一第二氮化矽層,並於該重摻雜矽薄膜與該第二氮化矽層上形成裸露處使該矽基板露出於該重摻雜矽薄膜與該第二氮化矽外;以及(7)在該矽基板的該正面形成一正面電極,而在該背面形成一背面電極。 A method for manufacturing a solar cell having an anti-reflection surface, comprising the steps of: (1) providing a germanium substrate having a front side and a back side; and (2) forming a first tantalum nitride layer on the front side; Laying a nanosphere on the tantalum nitride layer, using a nanosphere as a first etching mask; (4) etching the tantalum nitride layer by a reactive ion etching technique to form an etching window on the tantalum nitride layer (5) removing the nanosphere; (6) etching the germanium substrate to form a deep concave structure, wherein step (6) further comprises the following steps: (6-1') forming a heavily doped on the germanium substrate a doped film; and (6-2') forming a second tantalum nitride layer on the heavily doped germanium film, and forming a bare place on the heavily doped germanium film and the second tantalum nitride layer The germanium substrate is exposed outside the heavily doped germanium film and the second tantalum nitride; and (7) a front electrode is formed on the front surface of the germanium substrate, and a back electrode is formed on the back surface. 如申請專利範圍第1項所述的方法,其中步驟(2)的該氮化矽層是以射頻濺鍍的方式製造。 The method of claim 1, wherein the tantalum nitride layer of step (2) is fabricated by radio frequency sputtering. 如申請專利範圍第1項所述的方法,其中步驟(1)更包含一步驟(1-1):在該矽基板的正面摻雜五價元素做氮離子擴散。 The method of claim 1, wherein the step (1) further comprises a step (1-1): doping a pentavalent element on the front side of the germanium substrate for nitrogen ion diffusion. 如申請專利範圍第1項所述的方法,其中步驟(5)更包括步驟(5-1):於該矽基板的背面形成一導電層。 The method of claim 1, wherein the step (5) further comprises the step (5-1): forming a conductive layer on the back side of the germanium substrate. 如申請專利範圍第4項所述的方法,其中步驟 (5-1)的該導電層係用來作為光輔助電化學蝕刻產生電場之用。 The method of claim 4, wherein the method The conductive layer of (5-1) is used for generating an electric field as a photo-assisted electrochemical etching. 如申請專利範圍第1項所述的方法,其中步驟(7)所述的正面電極,是位於該裸露處因而穿過該重摻雜矽薄膜與該第二氮化矽層而與該矽基板電連接。 The method of claim 1, wherein the front electrode of the step (7) is located at the bare portion and thus passes through the heavily doped germanium film and the second tantalum nitride layer and the germanium substrate Electrical connection. 如申請專利範圍第1項所述的方法,其中步驟(6)是以光輔助電化學蝕刻的方式,蝕刻該矽基板。 The method of claim 1, wherein the step (6) etches the germanium substrate in a photo-assisted electrochemical etching manner. 如申請專利範圍第7項所述的方法,其中在步驟(6)之前,更包含一步驟:在該矽基板上預蝕出凹坑。 The method of claim 7, wherein before step (6), further comprising the step of pre-etching the pits on the substrate. 如申請專利範圍第8項所述的方法,其中該凹坑係以非等向性濕式蝕刻來製造。 The method of claim 8, wherein the pit is fabricated by anisotropic wet etching. 一種具有抗反射表面的太陽電池的製造方法,包括下列步驟:(1)提供一矽基板,該矽基板具有正面與背面;(2)舖設奈米球於該正面上,並以該奈米球為蝕刻遮罩;(3)蝕刻該矽基板用以形成深凹型結構;(4)移除該奈米球;(5-a’)於該矽基板上形成一重摻雜矽薄膜;(5-b’)於該重摻雜矽薄膜上形成一第二氮化矽層,並於該重摻雜矽薄膜與該第二氮化矽層上形成裸露處使該矽基板曝露於該重摻雜矽薄膜與該第二氮化矽外;(5-c’)於該矽基板的正面形成一正面電極,其中該正面電極通過該裸露處而與該矽基板電連接;以及 (5-d’)於該矽基板的背面形成一背面電極。 A method for manufacturing a solar cell having an anti-reflection surface, comprising the steps of: (1) providing a substrate having a front side and a back side; (2) laying a nanosphere on the front surface and using the nano ball For etching the mask; (3) etching the germanium substrate to form a deep concave structure; (4) removing the nanosphere; (5-a') forming a heavily doped germanium film on the germanium substrate; B') forming a second tantalum nitride layer on the heavily doped germanium film, and forming a bare place on the heavily doped germanium film and the second tantalum nitride layer to expose the germanium substrate to the heavily doped a ruthenium film and the second tantalum nitride; (5-c') forming a front electrode on a front surface of the ruthenium substrate, wherein the front electrode is electrically connected to the ruthenium substrate through the bare portion; (5-d') A back electrode is formed on the back surface of the substrate. 如申請專利範圍第10項所述的方法,其中步驟(3)是以高密度電漿反應式離子蝕刻(ICP-RIE)技術蝕刻該矽基板。 The method of claim 10, wherein the step (3) is etching the tantalum substrate by a high density plasma reactive ion etching (ICP-RIE) technique. 如申請專利範圍第10項所述的方法,其中該矽基板為N型矽,則該重摻雜矽薄膜則為P型矽。 The method of claim 10, wherein the ruthenium substrate is an N-type ruthenium, and the heavily doped ruthenium film is a P-type ruthenium. 如申請專利範圍第10項所述的方法,其中該矽基板為P型矽,則該重摻雜矽薄膜則為N型矽。The method of claim 10, wherein the germanium substrate is a P-type germanium, and the heavily doped germanium film is an N-type germanium.
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