TWI590479B - Golden single-crystal silicon solar cells with high reflectivity and panels containing the same - Google Patents
Golden single-crystal silicon solar cells with high reflectivity and panels containing the same Download PDFInfo
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- Y—GENERAL 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
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本發明係關於一種可同時具有產業上可接受的轉換效率並產生視覺上令人滿意明亮金屬光澤之高反射率金色單晶矽太陽能電池及包含該電池之面板。 The present invention relates to a high reflectivity gold single crystal germanium solar cell that can simultaneously have an industrially acceptable conversion efficiency and produce a visually satisfactory bright metallic luster and a panel comprising the same.
矽太陽能電池為現今廣泛使用之太陽能電池之一,其設計係使用經n型或p型電荷載體摻雜之矽晶片,將該等經n型或p型電荷載體摻雜後之矽晶片彼此接觸形成具有p/n接面作為光電轉換基材,透過光子入射該光電轉換基材之表面以產生光電效應,形成電流。而具有高轉換效率之太陽能電池係該領域從業人員的開發目標,矽太陽能電池之轉換效率受有效入射光子量影響。為降低入射光子反射量,進而提高太陽能電池轉換效率,先前技術係透過以蝕刻製程粗糙化光電轉換基材(如單晶矽光電轉換基材,又稱原片)表面並於其上設置抗反射層。矽太陽能電池因受限於可有效降低光子反射量而使太陽能電池達到高轉換效率之抗反射層材料種類與厚度,其外觀通常呈現單調暗藍色系,如Jenny Nelson於2003年所著教科書「The Physics of Solar Cells」已揭示矽基太陽能電池的抗反射覆蓋層通常對太陽輻射強之紅光最佳化,而在藍光區間反射變多。基於此原因,矽基太陽能電池通常呈現紫色或藍色。目前市售之單晶矽高效太陽能電池(轉換效率 >20%),其表面均為單調暗藍色系,如圖一所示。然而,在各國政府推廣在建築物之屋頂或外牆安裝太陽能電池或面板之際,為同時兼顧美觀及電池轉換效率,須開發具有不同顏色之太陽能電池或面板作為建築設計或環境顏色之搭配。惟為了保有高轉換效率,現今所開發之彩色太陽能電池仍以低反射率之彩色太陽能電池為主,其雖可展現不同於先前技術之紫色或藍色的色彩,但其展現的色彩仍屬暗色系列。因此,開發具有明亮色彩(如具有明亮金屬光澤之金色)之太陽能電池是需要的。 矽Solar cell is one of the solar cells widely used today, and its design uses a germanium wafer doped with n-type or p-type charge carriers, and the germanium wafers doped with n-type or p-type charge carriers are in contact with each other. A p/n junction is formed as a photoelectric conversion substrate, and photons are incident on the surface of the photoelectric conversion substrate to generate a photoelectric effect to form a current. The solar cell with high conversion efficiency is the development goal of practitioners in the field, and the conversion efficiency of the solar cell is affected by the effective incident photon amount. In order to reduce the amount of incident photon reflection, and thereby improve the solar cell conversion efficiency, the prior art is to roughen the surface of the photoelectric conversion substrate (such as a single crystal germanium photoelectric conversion substrate, also known as the original film) by an etching process and to provide anti-reflection thereon. Floor.矽 Solar cells are limited by the type and thickness of the anti-reflective layer material that can effectively reduce the amount of photon reflection, so that the solar cell achieves high conversion efficiency. The appearance of the solar cell is usually monotonous dark blue, as taught by Jenny Nelson in 2003. The Physics of Solar Cells has revealed that anti-reflective coatings for germanium-based solar cells are generally optimized for red light with strong solar radiation, while reflections are more common in the blue light region. For this reason, germanium based solar cells typically exhibit a purple or blue color. Currently marketed single crystal germanium high efficiency solar cells (conversion efficiency) >20%), the surface is monotonous dark blue, as shown in Figure 1. However, in the case of national governments promoting the installation of solar cells or panels on the roof or exterior walls of buildings, in order to achieve both aesthetic and battery conversion efficiency, solar cells or panels of different colors must be developed as a combination of architectural design or environmental color. However, in order to maintain high conversion efficiency, the color solar cells developed today are still dominated by low-reflection color solar cells, which can exhibit different colors from the purple or blue colors of the prior art, but the colors they display are still dark. series. Therefore, the development of solar cells with bright colors such as gold with a bright metallic luster is needed.
一物體的表面反射率越高,進入觀察者眼中的光量亦越高,觀察者可察覺色彩變為更明亮。然而,對太陽能電池而言,其表面反射率提高,即表示進入電池元件的光量相對減少,電池轉換效率因而下降。故如何在太陽能電池之轉換效率與其外觀色彩明亮度間取捨,為一重要課題。 The higher the surface reflectance of an object, the higher the amount of light entering the viewer's eye, and the observer can perceive that the color becomes brighter. However, for solar cells, the surface reflectance is increased, that is, the amount of light entering the battery element is relatively reduced, and the battery conversion efficiency is thus lowered. Therefore, how to choose between the conversion efficiency of solar cells and the brightness of their appearance is an important issue.
又物體對光之反射程度受該物體之受光表面形貌(如表面平坦程度)影響。於太陽能電池製程中,通常以蝕刻或化學機械研磨方法改變原片之表面形貌。蝕刻製程依其所使用之蝕刻液種類分為鹼蝕刻及酸蝕刻,目前針對單晶矽產業界多僅採用鹼蝕刻(其蝕刻液主要成份為氫氧化鉀),藉由在原片表面產生特殊紋理(texture),粗糙化原片表面,進而減少後續所形成之太陽能電池之表面光反射率,此製程雖可增加太陽能電池之轉換效率,但卻使得其外觀色彩更為暗沉。 The degree of reflection of the object on the light is affected by the surface topography of the object (such as the flatness of the surface). In the solar cell process, the surface morphology of the original sheet is usually changed by etching or chemical mechanical polishing. The etching process is divided into alkali etching and acid etching according to the type of etching liquid used. Currently, only the alkali etching (the main component of the etching liquid is potassium hydroxide) is used for the single crystal germanium industry, and a special texture is generated on the surface of the original sheet. (texture), roughening the surface of the original sheet, thereby reducing the surface light reflectivity of the subsequently formed solar cell. Although this process can increase the conversion efficiency of the solar cell, it makes the appearance color darker.
中華民國發明專利申請案TW 201445748已揭示一種彩色太陽能電池,其係透過於抗反射層上設置二或多層透明無機介電質層,其中該二或多層透明無機介電質層包含至少一層由鈦的氧化物所構成的第一透明無機介電質層,使太陽能電池產生不同的反射光譜進而展現多樣化色彩。然而,此太陽能電池之目的並非著重於提高太陽能電池之高反射率及色彩明亮度。 PCT Patent Application No. TW 201445748 discloses a color solar cell which is provided with two or more transparent inorganic dielectric layers disposed on an antireflection layer, wherein the two or more transparent inorganic dielectric layers comprise at least one layer of titanium The first transparent inorganic dielectric layer formed by the oxide causes the solar cell to generate different reflection spectra to exhibit diverse colors. However, the purpose of this solar cell is not to focus on improving the high reflectivity and color brightness of solar cells.
新型專利TW M493153雖已揭示一種金色結晶矽太陽能電池,然而其所採用之光電轉換基材為多晶矽,並非單晶矽,且其所得之太陽能電池外觀有明顯斑駁色塊,並未呈現單一且均勻之單色色彩分佈。 Although the novel patent TW M493153 has disclosed a gold-crystallized tantalum solar cell, the photoelectric conversion substrate used therein is polycrystalline germanium, which is not a single crystal germanium, and the obtained solar cell has obvious mottled color patches and does not appear single and uniform. Monochrome color distribution.
鑒於上述先前技術之問題,本發明之目的,係提供一種可同時具有產業上可接受的轉換效率及視覺上令人滿意之明亮高反射率金色單晶矽太陽能電池,其於波長560nm至630nm區間,具有大於20%之反射率。本發明亦提供一種包含該電池之面板,以豐富太陽能電池之色彩選擇,使太陽能電池能普及地為公眾所使用。 In view of the above prior art problems, it is an object of the present invention to provide a bright, high reflectance gold single crystal germanium solar cell which can simultaneously have an industrially acceptable conversion efficiency and is visually satisfactory, and has a wavelength ranging from 560 nm to 630 nm. With a reflectivity greater than 20%. The invention also provides a panel comprising the battery to enrich the color selection of the solar cell, so that the solar cell can be widely used by the public.
為達前述之目的,本發明提供一種金色單晶矽太陽能電池,其包含:高反射率單晶矽光電轉換基材;至少一層抗反射層,其設置於該高反射率單晶矽光電轉換基材上;一或多層透明無機介電層,其形成於該抗反射層之上方;及鈦氧化物層,其形成於該抗反射層之上方,其中該一或多層透明無機介電層具有介於約1.3至約2.2間之折射率,及該金色單晶矽太陽能電池於波長560nm至630nm區間,具有大於20%之反射率。 For the purpose of the foregoing, the present invention provides a gold single crystal germanium solar cell comprising: a high reflectivity single crystal germanium photoelectric conversion substrate; at least one antireflection layer disposed on the high reflectivity single crystal germanium photoelectric conversion substrate On the material; one or more transparent inorganic dielectric layers formed over the anti-reflective layer; and a titanium oxide layer formed over the anti-reflective layer, wherein the one or more transparent inorganic dielectric layers have a dielectric layer The refractive index between about 1.3 and about 2.2, and the gold single crystal germanium solar cell have a reflectance of greater than 20% in the wavelength range of 560 nm to 630 nm.
為達前述之目的,本發明係以酸蝕刻(其蝕刻液主要成份為氫氟酸)處理單晶矽原片表面,藉此移除單晶矽原片上因先前生產製程所形成之缺陷,得到一相較未經酸蝕刻處理者為平坦、高反射率的表面,以利產生兼具可接受的轉換效率及較先前技術之單晶太陽能電池明亮外觀之太陽能電池。 For the purpose of the foregoing, the present invention treats the surface of a single crystal crucible sheet by acid etching (the main component of the etching solution is hydrofluoric acid), thereby removing the defects formed on the single crystal crucible sheet due to the previous production process. A flat, high reflectivity surface compared to a non-acid etch process to produce a solar cell that combines acceptable conversion efficiencies with the brighter appearance of prior art monocrystalline solar cells.
本發明亦提供一種太陽能電池面板,其包含根據本發明之金色單晶矽太陽能電池所組成的電池模組;位於所述電池模組上的保護層;及位於所述保護層上的透明玻璃板。 The invention also provides a solar cell panel comprising a battery module composed of a gold single crystal germanium solar cell according to the invention; a protective layer on the battery module; and a transparent glass plate on the protective layer .
11‧‧‧透明無機介電層 11‧‧‧Transparent inorganic dielectric layer
12‧‧‧鈦氧化物層 12‧‧‧Titanium oxide layer
a‧‧‧抗反射層之厚度 a‧‧‧The thickness of the anti-reflection layer
AR‧‧‧抗反射層 AR‧‧‧Anti-reflective layer
b‧‧‧透明無機介電層之厚度 b‧‧‧Thickness of transparent inorganic dielectric layer
c‧‧‧鈦氧化物層之厚度 c‧‧‧Thickness of titanium oxide layer
S‧‧‧高反射率單晶矽光電轉換基材 S‧‧‧High reflectivity single crystal germanium photoelectric conversion substrate
圖1為市售之高效太陽能電池(轉換效率>20%),該電池表面為單 調暗藍色系。 Figure 1 is a commercially available high-efficiency solar cell (conversion efficiency >20%), the surface of the battery is single Darken the blue system.
圖2為根據本發明所得之高反射率金色單晶矽太陽能電池照片,其拍攝環境光源為室內日光燈,光強約800Lux,拍攝角度約為俯角90度,該太陽能電池係以大致上水平之方式平放。 2 is a photograph of a high reflectivity gold single crystal germanium solar cell obtained according to the present invention. The photographing ambient light source is an indoor fluorescent lamp having an intensity of about 800 Lux and a shooting angle of about 90 degrees. The solar cell is in a substantially horizontal manner. Lay flat.
圖3為根據本發明之高反射率金色單晶矽太陽能電池之剖面圖。 3 is a cross-sectional view of a high reflectivity gold single crystal germanium solar cell in accordance with the present invention.
圖4為實例1(a)、1(b)、1(c)及1(d)所得之原片(a)至(d)於400nm至800nm波長區間之反射率圖譜。 4 is a reflectance spectrum of the original sheets (a) to (d) obtained in Examples 1 (a), 1 (b), 1 (c), and 1 (d) in the wavelength range of 400 nm to 800 nm.
圖5為實例2(a)、2(b)、2(c)及2(d)之太陽能電池於400nm至800nm波長區間之反射率圖譜。 5 is a reflectance spectrum of the solar cells of Examples 2(a), 2(b), 2(c), and 2(d) in the wavelength range of 400 nm to 800 nm.
圖6為實例3-1之金色單晶矽太陽能電池於400nm至800nm波長區間之反射率圖譜。 6 is a reflectance spectrum of a gold single crystal germanium solar cell of Example 3-1 in a wavelength range of 400 nm to 800 nm.
圖7為實例3-2之金色單晶矽太陽能電池於400nm至800nm波長區間之反射率圖譜。 7 is a reflectance spectrum of a gold single crystal germanium solar cell of Example 3-2 in a wavelength range of 400 nm to 800 nm.
圖8(a)及8(b)為比較實例1之多晶矽彩色太陽能電池外觀及比較實例2之金色多晶矽太陽能電池外觀。 8(a) and 8(b) are the appearance of the polycrystalline germanium color solar cell of Comparative Example 1 and the appearance of the golden polycrystalline germanium solar cell of Comparative Example 2.
本文中所使用術語「約」意指包含如由一般熟習此項技術者所測定之特定值的可接受誤差,其部分地視如何量測或測定該值而定。 The term "about" as used herein is meant to include an acceptable error as the value determined by those skilled in the art, which is determined in part by how the value is measured or determined.
本文中所使用術語「無機介電」係指可被電極化的無機絕緣體。 The term "inorganic dielectric" as used herein refers to an inorganic insulator that can be electrodeized.
本文中所使用術語「原片」係指未經沉積無機介電物於其表面之矽太陽能電池。 The term "original sheet" as used herein refers to a tantalum solar cell on which the inorganic dielectric is not deposited on its surface.
本文中所使用術語「反射率」係由以一粗糙白色表面經積分球後所得之100%反射光量為基礎,計算太陽能電池之反射光量所得。 The term "reflectance" as used herein is calculated from the amount of reflected light of a solar cell based on the amount of 100% reflected light obtained by integrating a rough white surface with an integrating sphere.
本文中之反射率圖譜係以標準8度角絨面積分式反射率量測儀量測所得,該量測儀為一款可測量具有粗糙面之試片之反射率的儀器, 由里華科技股份有限公司設計而成。此儀器係根據ISO7724和DIN5033標準設計之新型反射率量測儀,其於太陽能電池領域中,常被使用在量測太陽能矽晶片之反射率,作為可有效地檢驗太陽能矽晶片的生產過程之量測儀。 The reflectance maps herein are measured using a standard 8 degree velvet area fractional reflectance meter, which is an instrument that measures the reflectivity of a test piece with a rough surface. Designed by Lihua Technology Co., Ltd. This instrument is a new reflectivity measuring instrument designed according to ISO7724 and DIN5033 standards. It is often used in the field of solar cells to measure the reflectivity of solar tantalum wafers as an effective measure of the production process of solar tantalum wafers. Measuring instrument.
反射率量測儀之基本配置方式為光電技術領域中之通常知識者所周知。本發明所採之反射率量測儀之配置係採用氙燈光源(其波長為250nm~2500nm、額定功率為75W、工作電流為5A)及一8°/d積分球,該積分球係用於量測試片全部的反射率,其包含散射與鏡射。該積分球之出光口直徑為20mm,取樣範圍直徑為25mm。氙燈光源與積分球呈90度角方式入射至積分球內,該積分球正下方可放置標準白板或待測試片,標準白板可為具有化學惰性的材料,其於波長400nm~1500nm反射率值達到99%以上,例如Ocean Optics,Inc所售之WS-1-SL Reflectance Standards。該積分球開口與標準白板或待測試片間之距離為0.3mm,反射光量的收集偵測器係位於積分球開口端夾角8度的位置,並經光纖連接至光譜儀,以Back-thinned type CCD組作為信號接收方式,其有效波長範圍:320nm~1074nm;解析度:1.45nm;精確度:10nm內<0.05%,將反射光於各波長的光量訊號傳至電腦,經計算獲得待測試片的反射率光譜。 The basic configuration of the reflectance meter is well known to those of ordinary skill in the art of optoelectronic technology. The reflectance measuring instrument adopted by the invention adopts a xenon lamp source (having a wavelength of 250 nm to 2500 nm, a rated power of 75 W, an operating current of 5 A) and an 8°/d integrating sphere, and the integrating sphere is used for the amount. The total reflectivity of the test piece, which includes scattering and mirroring. The diameter of the light exit port of the integrating sphere is 20 mm, and the sampling range diameter is 25 mm. The xenon lamp source and the integrating sphere are incident on the integrating sphere at a 90 degree angle. A standard whiteboard or a test piece can be placed directly below the integrating sphere. The standard whiteboard can be a chemically inert material, and the reflectance value reaches 400 nm to 1500 nm. More than 99%, such as WS-1-SL Reflectance Standards sold by Ocean Optics, Inc. The distance between the integrating sphere opening and the standard whiteboard or the piece to be tested is 0.3 mm, and the reflected light amount of the collecting detector is located at an angle of 8 degrees from the open end of the integrating sphere, and is connected to the spectrometer via the optical fiber to the Back-thinned type CCD. The group is used as the signal receiving mode, and its effective wavelength range is 320nm~1074nm; resolution: 1.45nm; accuracy: <0.05% within 10nm, the light signal of reflected light at each wavelength is transmitted to the computer, and the sample to be tested is obtained by calculation. Reflectance spectrum.
該反射率量測儀之可量測波長範圍為400nm~1000nm,量測方式為先量測標準白板的反射光量作為標準值,隨後量測待測試片的反射光量。測試片的反射率光譜係由測試片於各波長的反射光量相較於標準白板各波長的反射光量之比值得到。 The reflectance measuring instrument has a measurable wavelength range of 400 nm to 1000 nm. The measuring method is to first measure the amount of reflected light of the standard whiteboard as a standard value, and then measure the amount of reflected light of the to-be-tested piece. The reflectance spectrum of the test piece is obtained from the ratio of the amount of reflected light of each test wavelength at each wavelength to the amount of reflected light of each wavelength of the standard whiteboard.
理論上,本發明之單晶矽太陽能電池金色色彩係由入射光經過形成設置於抗反射層上之鈦氧化物層及透明無機介電質層時,於各膜層介面產生的反射光,經各層折射與厚度組合產生之光程差互相干涉下所形成。又由於本發明採用經酸蝕刻之單晶矽原片作為光電轉換基 材,故近距離觀察本發明之金色單晶矽太陽能電池並不會觀察到先前技術之經鹼蝕刻之多晶矽太陽能電池上之斑駁色塊(如圖8(b)所示)。本發明之金色單晶矽太陽能電池外觀如圖2所示,其拍攝環境光源為室內日光燈,光強約800Lux,拍攝角度約為俯角90度,該太陽能電池係以大致上水平之方式平放,其所呈現之金色具有明亮之金屬光澤。本發明之金色包含習知之金色色彩,並不以圖2所示之金色為限。本發明之金色包含但不限於,具有金屬光澤之金色、黃金般之黃金色、太陽光之金色、玫瑰金色及銅金色。 Theoretically, the golden color of the single crystal germanium solar cell of the present invention is reflected light generated on the interface of each film layer when the incident light passes through the titanium oxide layer and the transparent inorganic dielectric layer formed on the antireflection layer. The optical path difference generated by the combination of the refraction and the thickness of each layer is formed by mutual interference. Further, since the present invention employs an acid-etched single crystal ruthenium original sheet as a photoelectric conversion group Therefore, the close observation of the gold single crystal germanium solar cell of the present invention does not obviate the mottled color block on the prior art alkali-etched polycrystalline silicon solar cell (as shown in Fig. 8(b)). The appearance of the golden single crystal germanium solar cell of the present invention is as shown in FIG. 2, and the shooting environment light source is an indoor fluorescent lamp with an intensity of about 800 Lux and a shooting angle of about 90 degrees. The solar cell is laid flat in a substantially horizontal manner. The gold it presents has a bright metallic luster. The gold of the present invention contains conventional golden colors and is not limited to the gold shown in FIG. The gold of the present invention includes, but is not limited to, metallic gold, gold-like gold, golden sun, rose gold, and copper gold.
又太陽能電池之外觀色彩係由入射光於各膜層介面折射及/或反射後,最終進入觀察者眼中反射光波長分佈所決定,其外觀色彩受入射光之入射角、觀察者與太陽能電池間之角度等因素影響。亦即,正面俯視觀察太陽能電池所得之外觀色彩與側向傾斜地觀察太陽能電池所得之外觀色彩可為不同。 The appearance color of the solar cell is determined by the wavelength distribution of the reflected light in the observer's eye after the incident light is refracted and/or reflected by the interface of each film layer, and the appearance color is affected by the incident angle of the incident light, between the observer and the solar cell. Factors such as angles. That is, the appearance color obtained by looking at the solar cell in a front view and the appearance color obtained by observing the solar cell in a laterally inclined manner may be different.
本發明提供一種高反射率金色單晶矽太陽能電池,其包含:高反射率單晶矽光電轉換基材;至少一層抗反射層,其設置於該高反射率單晶矽光電轉換基材上;一或多層透明無機介電層,其形成於該抗反射層之上方;及鈦氧化物層,其形成於該抗反射層之上方,其中該一或多層透明無機介電層具有介於約1.3至約2.2間之折射率,及該金色單晶矽太陽能電池於波長560nm至630nm區間具有大於20%之反射率。 The present invention provides a high reflectivity gold single crystal germanium solar cell comprising: a high reflectivity single crystal germanium photoelectric conversion substrate; at least one antireflection layer disposed on the high reflectivity single crystal germanium photoelectric conversion substrate; One or more transparent inorganic dielectric layers formed over the anti-reflective layer; and a titanium oxide layer formed over the anti-reflective layer, wherein the one or more transparent inorganic dielectric layers have a relationship of about 1.3 The refractive index to about 2.2, and the gold single crystal germanium solar cell have a reflectance of greater than 20% in the wavelength range of 560 nm to 630 nm.
不同於先前技術之太陽能電池之原片均經粗糙化之處理,本發明之單晶矽原片之表面係經可減少表面粗糙度處理,如酸蝕刻(其蝕刻液主要成份為氫氟酸)或化學機械研磨方法,藉此移除單晶矽原片上因先前生產製程所形成之缺陷,得到一較為平坦且具有較高反射率的表面,作為後續製作本發明之金色單晶矽太陽能電池之基材。本發明較佳係使用酸蝕刻處理原片。 Different from the prior art solar cell, the original film is subjected to roughening treatment, and the surface of the single crystal bismuth original film of the present invention can reduce surface roughness treatment, such as acid etching (the main component of the etching liquid is hydrofluoric acid) Or a chemical mechanical polishing method, thereby removing the defects formed on the single crystal crucible sheet due to the previous production process, to obtain a relatively flat surface having a higher reflectance, as a subsequent preparation of the golden single crystal germanium solar cell of the present invention. Substrate. The present invention preferably uses an acid etching treatment of the original sheet.
根據本發明之一具體實施例,本發明之金色單晶矽太陽能電池中之鈦氧化物層係位於該一或多層透明無機介電層之上方。根據本發明之另一具體實施例,本發明之金色單晶矽太陽能電池包含至少兩層透明無機介電層,該鈦氧化物層係位於該等透明無機介電層中至少一者上。 In accordance with an embodiment of the present invention, a titanium oxide layer in a gold single crystal germanium solar cell of the present invention is positioned over the one or more transparent inorganic dielectric layers. In accordance with another embodiment of the present invention, a gold single crystal germanium solar cell of the present invention comprises at least two transparent inorganic dielectric layers, the titanium oxide layer being on at least one of the transparent inorganic dielectric layers.
根據本發明之另一具體實施例,本發明之金色單晶矽太陽能電池依序於該抗反射層上設置有一層鈦氧化物層及一層透明無機介電層。 According to another embodiment of the present invention, the golden single crystal germanium solar cell of the present invention is provided with a titanium oxide layer and a transparent inorganic dielectric layer on the antireflection layer.
根據本發明之一具體實施例,本發明之金色單晶矽太陽能電池包含兩層透明無機介電層(即第一透明無機介電層及第二透明無機介電層)及鈦氧化物層,其係以第一透明無機介電層、鈦氧化物層及第二透明無機介電層之順序形成於該抗反射層上方。 According to an embodiment of the present invention, the golden single crystal germanium solar cell of the present invention comprises two transparent inorganic dielectric layers (ie, a first transparent inorganic dielectric layer and a second transparent inorganic dielectric layer) and a titanium oxide layer. It is formed above the anti-reflection layer in the order of the first transparent inorganic dielectric layer, the titanium oxide layer and the second transparent inorganic dielectric layer.
根據本發明之一具體實施例,本發明之金色單晶矽太陽能電池於波長530nm至630nm區間,具有大於20%,較佳為大於25%,更佳為大於30%之反射率。 In accordance with an embodiment of the present invention, the gold single crystal germanium solar cell of the present invention has a reflectance of greater than 20%, preferably greater than 25%, and more preferably greater than 30%, in the wavelength range from 530 nm to 630 nm.
本發明之鈦氧化物層係由未經摻雜之鈦氧化物所形成。該鈦氧化物層具有介於約20nm至約120nm,較佳為約30nm至約100nm,更佳為約50nm至約80nm之間之厚度,其具有介於約2.2至約2.6間之折射率。 The titanium oxide layer of the present invention is formed from undoped titanium oxide. The titanium oxide layer has a thickness of between about 20 nm and about 120 nm, preferably between about 30 nm and about 100 nm, more preferably between about 50 nm and about 80 nm, and has a refractive index between about 2.2 and about 2.6.
本發明之一或多層透明無機介電層中各者獨立地由具有介於約1.3至約2.2之間,較佳為約1.5至約2.0之間之折射率之透明無機介電質所組成。該一或多層透明無機介電層中各者獨立地具有介於約1nm至約200nm之間,較佳係介於約10nm至180nm之間,更佳係介於約100nm至150nm之間之厚度。 Each of the one or more layers of the transparent inorganic dielectric layer of the present invention is independently composed of a transparent inorganic dielectric having a refractive index of between about 1.3 and about 2.2, preferably between about 1.5 and about 2.0. Each of the one or more transparent inorganic dielectric layers independently has a thickness of between about 1 nm and about 200 nm, preferably between about 10 nm and 180 nm, more preferably between about 100 nm and 150 nm. .
該一或多層透明無機介電質中各者獨立地係選自由經鋁摻雜之鈦的氧化物、氧化銦錫、未經摻雜之鋅的氧化物、經鋁或經鋁鎵共摻 雜之鋅的氧化物及矽的氮化物所組成之群。該一或多層透明無機介電層中各者獨立地較佳係選自由經鋁摻雜之鋅的氧化物、氧化銦錫、氧化鋅及氮化矽所組成之群。更佳的是,該一或多層透明無機介電層中至少一者係由經鋁摻雜之鋅的氧化物所形成。 Each of the one or more layers of transparent inorganic dielectric is independently selected from the group consisting of oxides of aluminum doped with aluminum, indium tin oxide, oxides of undoped zinc, co-doped with aluminum or aluminum gallium A group of hetero-zinc oxides and niobium nitrides. Each of the one or more transparent inorganic dielectric layers is independently selected from the group consisting of aluminum-doped zinc oxide, indium tin oxide, zinc oxide, and tantalum nitride. More preferably, at least one of the one or more transparent inorganic dielectric layers is formed from an oxide of zinc doped with aluminum.
根據本發明之一具體實施例,本發明提供一種金色單晶矽太陽能電池,在太陽光下呈現具有明亮金屬光澤之金色,如圖2,其製作方法包含以下步驟: According to an embodiment of the present invention, the present invention provides a golden single crystal germanium solar cell which exhibits a golden color with a bright metallic luster under sunlight, as shown in FIG. 2, the manufacturing method comprising the following steps:
1.提供一單晶矽晶片基材(即原片),僅以酸蝕刻去除<100>或<110>方向單晶矽表面缺陷,或以酸蝕刻及鹼蝕刻去除<111>方向單晶矽表面缺陷,可得到具有可接受之光滑表面且於可見光區400nm至500nm波長區間具有大於30%之高反射率之單晶矽光電轉換基材。 1. Providing a single crystal germanium wafer substrate (ie, an original sheet), removing only the surface defects of the single crystal germanium in the <100> or <110> direction by acid etching, or removing the single crystal germanium in the <111> direction by acid etching and alkali etching. Surface defects provide a single crystal germanium photoelectric conversion substrate having an acceptable smooth surface and having a high reflectance of more than 30% in the wavelength range of 400 nm to 500 nm in the visible light region.
2.於該單晶矽光電轉換基材上形成至少一層抗反射層。 2. Forming at least one antireflection layer on the single crystal germanium photoelectric conversion substrate.
3.於該抗反射層上形成鈦氧化物層。 3. Forming a titanium oxide layer on the antireflective layer.
4.於步驟3後或於步驟2及3之間形成一或多層透明無機介電層中至少一者。 4. Forming at least one of the one or more transparent inorganic dielectric layers after step 3 or between steps 2 and 3.
圖3為根據本發明之具體態樣之金色單晶矽太陽能電池之剖面圖,其包含:具有可接受之光滑表面且具有高反射率(400nm至500nm波長區間,反射率大於30%)之高反射率單晶矽光電轉換基材(S);至少一層抗反射層(AR),其形成於該高反射率單晶矽光電轉換基材上;一層透明無機介電質層(11)及鈦氧化物層(12)。 3 is a cross-sectional view of a gold single crystal germanium solar cell according to a specific aspect of the present invention, comprising: an acceptable smooth surface and a high reflectance (wavelength range of 400 nm to 500 nm, reflectance greater than 30%) Reflectivity single crystal germanium photoelectric conversion substrate (S); at least one antireflection layer (AR) formed on the high reflectivity single crystal germanium photoelectric conversion substrate; a transparent inorganic dielectric layer (11) and titanium Oxide layer (12).
適用於本發明之經蝕刻處理前之光電轉換基材,係技藝中所知之單晶矽材料。前述之蝕刻處理亦可改為化學機械研磨方法。 The photoelectric conversion substrate suitable for use in the etching process of the present invention is a single crystal germanium material known in the art. The aforementioned etching treatment can also be changed to a chemical mechanical polishing method.
適用於本發明作為抗反射層之材料,亦係技藝中所知可用於太陽能電池的任何適合的材料,包括由SiNx所形成的單層SiNx薄膜,或包含兩層氮與矽元素比例不同之SiNx薄膜,x可為1.1至1.3之間之數 值。 The present invention is suitable as a material for the antireflection layer, any suitable material system also known in the art may be used for a solar cell, including monolayer SiN x film formed by the SiN x, or containing element nitrogen to silicon ratio of two different For SiN x films, x can be between 1.1 and 1.3.
根據本發明,用於形成抗反射層、鈦氧化物層及透明無機介電層可為任何技藝中所已知之方法,其包括磁控直流濺鍍法(DC Magnetron Sputtering)、蒸鍍法(evaporation)、濺鍍法(sputtering)、化學氣相沉積法(CVD)、塗佈法(coating)或其他熟習該項技藝者認為適切可行之方法。 The method for forming the antireflection layer, the titanium oxide layer, and the transparent inorganic dielectric layer according to the present invention may be any method known in the art, including DC Magnetron Sputtering, evaporation (evaporation). ), sputtering, chemical vapor deposition (CVD), coating, or other methods known to those skilled in the art to be suitable.
根據本發明之一具體態樣,本發明可提供一種金色單晶矽太陽能電池,其可見光波段反射光譜顯示,其於波長560至630區間之平均反射率,具有大於20%之反射率。觀察者在正面垂直觀察或以一特定角度斜向觀察本發明之金色單晶矽太陽能電池之方式下,均可觀察到金色色彩。以大致上水平之方式平放之本發明之金色單晶矽太陽能電池為例,觀察者可在觀察者俯視角(即進入觀察者眼中之觀察者反射光與水平線之夾角)為約10度至約90度之範圍內,較佳約30度至約90度之範圍內,觀察到金色色彩。 According to an embodiment of the present invention, the present invention provides a gold single crystal germanium solar cell whose visible light band reflectance spectrum exhibits an average reflectance in the wavelength range of 560 to 630 having a reflectance of more than 20%. The observer can observe the golden color of the golden single crystal germanium solar cell of the present invention by observing the vertical side of the front side obliquely or at a specific angle. Taking the gold single crystal germanium solar cell of the present invention laid flat in a substantially horizontal manner as an example, the observer can be at an angle of view of the observer at a viewing angle (ie, the angle between the reflected light of the observer entering the observer's eye and the horizontal line) is about 10 degrees. A golden color is observed in the range of about 90 degrees, preferably about 30 degrees to about 90 degrees.
本發明之金色單晶矽太陽能電池具有產業上可接受之轉換效率,其至少大於14%。 The gold single crystal germanium solar cell of the present invention has an industrially acceptable conversion efficiency of at least greater than 14%.
本發明另提供包含上述太陽能電池之面板,其係經由於本發明之彩色太陽能電池上依序放置保護層與透明層封裝後所形成。適用於本發明之保護層可為技藝中已知之封裝材料,例如可為乙基醋酸乙基酯(ethylene vinyl acetate,EVA)、聚乙烯縮丁醛(polyvinyl butyral,PVB)或其他熟習該項技藝者認為適切可行之類似物,其可保護太陽能電池免於暴露於水或溼氣中。適用於本發明太陽能電池面板之透明層亦可為技藝中已知之材料,例如玻璃。 The present invention further provides a panel comprising the above solar cell, which is formed by sequentially placing a protective layer and a transparent layer on the color solar cell of the present invention. The protective layer suitable for use in the present invention may be an encapsulating material known in the art, and may be, for example, ethylene vinyl acetate (EVA), polyvinyl butyral (PVB) or other familiar art. Suitable analogs are considered to protect solar cells from exposure to water or moisture. The transparent layer suitable for use in the solar cell panel of the present invention may also be a material known in the art, such as glass.
以下實施例將針對本發明提供進一步之說明,並非用以限制本發明之保護範圍。 The following examples are provided to further illustrate the invention and are not intended to limit the scope of the invention.
酸蝕刻溶液為濃度3%~5%氫氟酸。 The acid etching solution is a concentration of 3% to 5% hydrofluoric acid.
鹼蝕刻溶液為濃度0.9%~1.1%氫氧化鉀。 The alkali etching solution is a concentration of 0.9% to 1.1% potassium hydroxide.
鹼蝕刻溶液為濃度0.9%~1.1%氫氧化鉀。 The alkali etching solution is a concentration of 0.9% to 1.1% potassium hydroxide.
酸蝕刻溶液為濃度3%~5%氫氟酸。 The acid etching solution is a concentration of 3% to 5% hydrofluoric acid.
以反射率量測儀量測上述(a)至(d)之原片於400nm至800nm波長區間之反射率,所得結果如圖4所示。 The reflectance of the original sheets of the above (a) to (d) in the wavelength range of 400 nm to 800 nm was measured by a reflectance meter, and the results are shown in Fig. 4.
由圖4可知本發明之經酸蝕刻之單晶矽原片(d)於400nm至500nm波長區間內具有大於30%之高反射率,在可見光區間內(400nm至750 nm),其反射率皆大於10%。然而,先前技術經鹼蝕刻之單晶矽原片(c)於400nm至500nm波長區間之反射率均未超過20%。於400nm至500nm波長區間,本發明之經酸蝕刻之單晶矽原片(d)之反射率係先前技術經鹼蝕刻之單晶矽原片(c)的至少1.5倍。另外,觀察多晶矽原片(a)及(b),於400nm至500nm波長區間內之反射率圖譜可知,先前技術之經鹼蝕刻之多晶矽原片(b)僅於約400nm至440nm波長區間內觀察到大於30%反射率,而先前技術之經酸蝕刻之多晶矽原片(a)於400nm至500nm波長區間之反射率均未超過30%。 4, the acid-etched single crystal germanium film (d) of the present invention has a high reflectance of more than 30% in the wavelength range of 400 nm to 500 nm, in the visible light range (400 nm to 750). Nm), its reflectivity is greater than 10%. However, the reflectance of the prior art alkali-etched single crystal bismuth original sheet (c) in the wavelength range of 400 nm to 500 nm did not exceed 20%. The reflectance of the acid-etched single crystal germanium sheet (d) of the present invention is at least 1.5 times that of the prior art alkali-etched single crystal germanium sheet (c) in the wavelength range of 400 nm to 500 nm. In addition, observing the reflectance spectra of the polycrystalline bismuth original sheets (a) and (b) in the wavelength range of 400 nm to 500 nm, it is known that the prior art alkali-etched polycrystalline bismuth original sheet (b) is observed only in the wavelength range of about 400 nm to 440 nm. To a reflectance greater than 30%, the reflectivity of the prior art acid-etched polycrystalline germanium (a) in the 400 nm to 500 nm wavelength range does not exceed 30%.
於上述實例1(a)至1(d)之原片上依序以磁控直流濺鍍法形成經鋁摻雜之鋅的氧化物及鈦氧化物層,獲得實例2(a)、2(b)、2(c)及2(d)之太陽能電池。以反射率量測儀量測上述(a)至(d)之太陽能電池於400nm至800nm波長區間之反射率,所得結果如圖5所示。 On the original sheets of the above Examples 1 (a) to 1 (d), an aluminum-doped zinc oxide and a titanium oxide layer were sequentially formed by magnetron DC sputtering to obtain Examples 2 (a) and 2 (b). ), 2(c) and 2(d) solar cells. The reflectance of the solar cells of the above (a) to (d) in the wavelength range of 400 nm to 800 nm was measured by a reflectance meter, and the results are shown in FIG. 5.
由圖5可知,相較於實例2(a)至2(c)之先前技術太陽能電池,本發明之太陽能電池(即於經酸蝕刻單晶矽原片上濺鍍經鋁摻雜之鋅的氧化物及鈦氧化物層後所得者),在550至800nm波長區間內具有顯著較高之反射率。於波長560nm至630nm區間,本發明之太陽能電池具有高於先前技術之經鹼蝕刻之單晶矽太陽能電池2(c)至少2.2倍之反射率。 As can be seen from Fig. 5, the solar cell of the present invention (i.e., the oxidation of aluminum doped zinc on the acid-etched single crystal germanium sheet) compared to the prior art solar cells of Examples 2(a) to 2(c) The material obtained after the titanium oxide layer has a significantly higher reflectance in the wavelength range of 550 to 800 nm. In the wavelength range of 560 nm to 630 nm, the solar cell of the present invention has a reflectance higher than that of the prior art alkali-etched single crystal germanium solar cell 2 (c) by at least 2.2 times.
僅以酸蝕刻去除<100>方向單晶矽表面缺陷後,可得一表面光滑的單晶矽光電轉換基材。於該基材上形成包含SiNx之抗反射層後其反射率大於25%,並以製造先前技術周知之藍色太陽能電池之標準製程,於其上依序以磁控直流濺鍍法形成經鋁摻雜之鋅的氧化物及鈦的氧化物層後,即形成本發明之高反射率金色單晶矽太陽能電池,各層之厚度與折射率列於下表1-1。以反射率量測儀測試該太陽能電池在 各波長之反射率,所得之結果如圖6所示。 After removing the surface defects of the single crystal germanium in the <100> direction by acid etching, a single crystal germanium photoelectric conversion substrate having a smooth surface can be obtained. Forming an anti-reflective layer containing SiN x on the substrate, the reflectance thereof is greater than 25%, and forming a standard process of a blue solar cell known in the prior art, sequentially forming a magnetically controlled DC sputtering method thereon. The high-reflectance gold single crystal germanium solar cell of the present invention is formed by the aluminum-doped zinc oxide and the titanium oxide layer, and the thickness and refractive index of each layer are shown in Table 1-1 below. The reflectance of the solar cell at each wavelength was measured by a reflectance meter, and the results obtained are shown in Fig. 6.
僅以酸蝕刻去除<100>方向單晶矽表面缺陷後,可得一表面光滑的單晶矽光電轉換基材。於該基材上形成包含SiNx之抗反射層後其反射率大於30%,以製造先前技術周知之藍色太陽能電池之標準製程,於其上以磁控直流濺鍍法形成經鋁摻雜之鋅的氧化物及鈦的氧化物層後,其中各層之堆疊順序、材料種類、厚度與折射率列於下表1-2,即形成本發明之高反射率金色單晶矽太陽能電池。以反射率量測儀測試該太陽能電池在各波長之反射率,所得之結果如圖7所示。 After removing the surface defects of the single crystal germanium in the <100> direction by acid etching, a single crystal germanium photoelectric conversion substrate having a smooth surface can be obtained. After forming an anti-reflective layer containing SiN x on the substrate, the reflectance thereof is greater than 30% to manufacture a standard process of a blue solar cell known in the prior art, and the aluminum-doped method is formed by magnetron DC sputtering. After the zinc oxide and the titanium oxide layer, the stacking order, material type, thickness and refractive index of each layer are listed in Table 1-2 below, that is, the high reflectivity gold single crystal germanium solar cell of the present invention is formed. The reflectance of the solar cell at each wavelength was measured by a reflectance meter, and the results obtained are shown in FIG.
在經酸蝕刻處理之多晶矽光電轉換基材上形成包含SiN1.1之抗反射層,以製造先前技術周知之藍色太陽能電池之標準製程,於其上依序以磁控直流濺鍍法形成鈦的氧化物及經鋁摻雜之鋅的氧化物,各層之厚度與折射率列於下表2。所得之多晶矽太陽能電池外觀色彩為如圖8(a)所示之磚紅色。 Forming an anti-reflective layer comprising SiN 1.1 on an acid-etched polycrystalline germanium photoelectric conversion substrate to produce a standard process of a blue solar cell known in the prior art, on which a titanium is formed by magnetron DC sputtering. The oxide and aluminum-doped zinc oxide, the thickness and refractive index of each layer are listed in Table 2 below. The resulting polycrystalline silicon solar cell has an appearance color of brick red as shown in Fig. 8(a).
在經鹼蝕刻之多晶矽光電轉換基材上形成包含氮化矽之抗反射層,以製造先前技術周知之藍色太陽能電池之標準製程,於其上依序以磁控直流濺鍍法形成經鋁摻雜之鋅的氧化物及鈦的氧化物,各層之厚度與折射率列於下表3。近距離觀察所得之多晶矽太陽能電池外觀色彩為如圖8(b)所示,其係具有明顯斑駁色塊之太陽能電池,並未呈現本發明之金色太陽能電池所具有之單一且均勻之金色色彩(如圖2所示)。又比較圖8(b)與本發明之金色太陽能電池之金色之彩度,本發明之金色太陽能電池所呈現之金色較為明亮,且具有金屬光澤。 Forming an anti-reflective layer comprising tantalum nitride on the alkali-etched polycrystalline germanium photoelectric conversion substrate to fabricate a standard process of a blue solar cell known in the prior art, and sequentially forming aluminum via magnetron DC sputtering The thickness of the doped zinc oxide and the oxide of titanium are shown in Table 3 below. The appearance of the polycrystalline silicon solar cell obtained by close observation is as shown in FIG. 8(b), which is a solar cell having a distinct mottled color block, and does not exhibit the single and uniform golden color of the golden solar cell of the present invention ( as shown in picture 2). Comparing Fig. 8(b) with the golden color of the golden solar cell of the present invention, the golden solar cell of the present invention exhibits a brighter gold color and a metallic luster.
11‧‧‧透明無機介電層 11‧‧‧Transparent inorganic dielectric layer
12‧‧‧鈦氧化物層 12‧‧‧Titanium oxide layer
a‧‧‧抗反射層之厚度 a‧‧‧The thickness of the anti-reflection layer
AR‧‧‧抗反射層 AR‧‧‧Anti-reflective layer
b‧‧‧透明無機介電層之厚度 b‧‧‧Thickness of transparent inorganic dielectric layer
c‧‧‧鈦氧化物層之厚度 c‧‧‧Thickness of titanium oxide layer
S‧‧‧高反射率單晶矽光電轉換基材 S‧‧‧High reflectivity single crystal germanium photoelectric conversion substrate
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