TWI401812B - Solar battery - Google Patents
Solar battery Download PDFInfo
- Publication number
- TWI401812B TWI401812B TW98146346A TW98146346A TWI401812B TW I401812 B TWI401812 B TW I401812B TW 98146346 A TW98146346 A TW 98146346A TW 98146346 A TW98146346 A TW 98146346A TW I401812 B TWI401812 B TW I401812B
- Authority
- TW
- Taiwan
- Prior art keywords
- solar cell
- amorphous germanium
- cell according
- substrate
- energy
- Prior art date
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Photovoltaic Devices (AREA)
Description
本發明是有關於一種太陽能電池，特別是指一種非晶矽太陽能電池。The present invention relates to a solar cell, and more particularly to an amorphous germanium solar cell.
太陽輻射之光譜，主要是以可見光為中心，其分佈範圍以0.3微米(μm)之紫外光到數微米之紅外光為主，若換算成光子的能量，則約在0.4eV(電子伏特)到4eV之間。一般來說，理想的太陽電池材料必須具備有下列特性：能隙在1.1eV到1.7eV之間、直接能隙半導體、組成的材料無毒性、可利用薄膜沉積的技術、並可大面積製造、有良好的光電轉換效率，及具有長時期的穩定性；而矽的能隙為1.12eV，且矽為間接能隙半導體，它對光的吸收性不好，所以矽在這方面並非是最理想的材料，但是矽為地球上蘊含量第二豐富的元素，且矽本身無毒性、其氧化物穩定又不具水溶性，因此目前太陽電池仍舊以矽為主要材料。The spectrum of solar radiation is mainly centered on visible light, and its distribution range is from 0.3 micrometer (μm) ultraviolet light to several micrometers of infrared light. If converted into photon energy, it is about 0.4eV (electron volt). Between 4eV. In general, an ideal solar cell material must have the following characteristics: an energy gap between 1.1 eV and 1.7 eV, a direct energy gap semiconductor, a non-toxic material, a thin film deposition technique, and a large-area fabrication. It has good photoelectric conversion efficiency and long-term stability. The energy gap of germanium is 1.12eV, and it is an indirect energy gap semiconductor. It has poor absorption of light, so it is not the best in this respect. The material, but it is the second most abundant element on the earth, and the ruthenium itself is non-toxic, its oxide is stable and not water-soluble, so the current solar cells still use bismuth as the main material.
矽原子依據不同的結晶方式，可區分成單晶矽、多晶矽及非晶矽，用單晶矽製成的太陽電池，效率高且性能穩定，目前已廣泛應用於太空及陸地上；多晶矽的矽原子堆積方式不只一種，它是由多種不同排列方向的單晶所組成，因其製程簡單、成本較低，因此，目前由多晶矽所製作出的太陽電池產量，已經逐漸超越單晶矽的太陽電池；非晶矽乃是指矽原子的排列非常紊亂，沒有規則可循。一般非晶矽是以電漿式化學氣相沈積法(Plasma Enhanced Chemical Vapor Deposition，簡稱PECVD)，在玻璃等基板上成長厚度約1微米(μm)左右的非晶矽薄膜，因為非晶矽對光的吸收性比矽強約500倍，所以對非晶矽而言只需要薄薄的一層就可以把光子的能量有效的吸收，而且不需要使用價格昂貴的結晶矽基板，改採用價格較便宜的玻璃、陶瓷或是金屬等基板，如此不僅可以節省大量的材料成本，也使得製作大面積的太陽電池成為可能。According to different crystallization modes, germanium atoms can be divided into single crystal germanium, polycrystalline germanium and amorphous germanium. Solar cells made of single crystal germanium are highly efficient and stable in performance, and have been widely used in space and on land; polycrystalline germanium There are more than one kind of atomic packing method. It is composed of a single crystal in a variety of different orientations. Because of its simple process and low cost, the solar cell production produced by polycrystalline germanium has gradually surpassed that of single crystal germanium. Amorphous germanium means that the arrangement of germanium atoms is very disordered and there are no rules to follow. Generally, the amorphous germanium is an amorphous germanium film having a thickness of about 1 micrometer (μm) grown on a substrate such as glass by a Plasma Enhanced Chemical Vapor Deposition (PECVD) because of the amorphous germanium pair. The absorption of light is about 500 times stronger than that of bare, so only a thin layer is needed for the amorphous germanium to absorb the energy of the photon, and it is not necessary to use an expensive crystalline germanium substrate, and the price is cheaper. The glass, ceramic or metal substrate can not only save a lot of material costs, but also make it possible to make a large area of solar cells.
參閱圖1，一般非晶矽太陽電池結構包含一基板11、一沉積成長於該基板11上的非晶矽薄膜12，及一與該非晶矽薄膜12相歐姆接觸的頂電極13。Referring to FIG. 1, a general amorphous germanium solar cell structure includes a substrate 11, an amorphous germanium film 12 deposited on the substrate 11, and a top electrode 13 in ohmic contact with the amorphous germanium film 12.
該基板11具有一由玻璃構成的基材111，及一形成在該基材111表面，且由氧化銦錫(ITO)構成的透明導電膜112，該非晶矽薄膜12形成在該透明導電膜112上並與該透明導電膜112為歐姆接觸，可在照光時以光伏特效應產生電能，該頂電極13形成在該非晶矽薄膜12上，可與該透明導電膜112相互配合將由該非晶矽薄膜12產生的電能向外輸出。The substrate 11 has a substrate 111 made of glass, and a transparent conductive film 112 formed on the surface of the substrate 111 and made of indium tin oxide (ITO). The amorphous germanium film 12 is formed on the transparent conductive film 112. And ohmic contact with the transparent conductive film 112, the electric energy can be generated by the photovoltaic effect when the light is irradiated, the top electrode 13 is formed on the amorphous germanium film 12, and the transparent conductive film 112 can cooperate with the amorphous germanium film. 12 The generated electric energy is output to the outside.
該非晶矽薄膜12具有經過摻雜(doping)而具有能階差的一P型(positive-type)半導體123、一N型(negative-type)半導體125，及一能階位於該P、N型半導體123、125的能階之間的純質(intrinsic)半導體124，當該非晶矽薄膜太陽電池照光時，該P型半導體123、純質半導體124，及N型半導體125會吸收光子產生電子-電洞對，電子-電洞對因內建電塲分離而形成光電流，該頂電極13與該透明導電膜112相互配合，將產生的光電流向外輸出。The amorphous germanium film 12 has a positive-type semiconductor 123 and a negative-type semiconductor 125 having a step difference by doping, and an energy level is located in the P and N types. An intrinsic semiconductor 124 between the energy levels of the semiconductors 123, 125, when the amorphous germanium thin film solar cell is illuminated, the P-type semiconductor 123, the pure semiconductor 124, and the N-type semiconductor 125 absorb photons to generate electrons - In the pair of holes, the electron-hole pair forms a photocurrent due to the separation of the built-in power, and the top electrode 13 and the transparent conductive film 112 cooperate to output the generated photocurrent to the outside.
但是近幾年非晶矽太陽能電池的生產比例有逐漸下滑的趨勢，而其中影響非晶矽太陽電池發展的主要因素就是穩定度的問題。由於非晶矽材料含有大量的缺陷以及未鍵結的矽懸鍵(Dangling Bond)，因此，在強烈的光線照射下，將會產生缺陷而導致電流下降(即所謂的Staebler-Wronski效應)，發生供電不穩定的問題，且隨著照光時間的增加，非晶矽薄膜太陽電池效率亦會快速衰減。雖然目前有採用雙重接面(a-Si/a-SiGe)電池來提升非晶矽薄膜太陽電池的穩定度，但是，仍有持續努力發展的空間。However, the production ratio of amorphous germanium solar cells has gradually declined in recent years, and the main factor affecting the development of amorphous germanium solar cells is the stability problem. Since amorphous germanium materials contain a large number of defects and unbonded Dangling Bonds, under intense light irradiation, defects will occur and current drops (the so-called Staebler-Wronski effect) occur. The problem of unstable power supply, and with the increase of illumination time, the efficiency of amorphous silicon solar cells will also decay rapidly. Although dual-junction (a-Si/a-SiGe) batteries are currently used to improve the stability of amorphous tantalum thin film solar cells, there is still room for continuous development.
因此，如何發展出可降低非晶矽薄膜不穩定的缺點及適合太陽能電池能隙的材料，以提升非晶矽太陽電池的穩定性及光利用效率，一直是太陽能技術領域者持續努力的重要目標。Therefore, how to develop the disadvantages of reducing the instability of the amorphous germanium film and the material suitable for the energy gap of the solar cell to improve the stability and light utilization efficiency of the amorphous germanium solar cell has been an important goal of the continuous efforts of the solar energy technology field. .
因此，本發明之目的，即在提供一種具有高穩定性，及高光利用率的非晶矽太陽能電池。Accordingly, it is an object of the present invention to provide an amorphous germanium solar cell having high stability and high light utilization efficiency.
於是，本發明一種太陽能電池，包含一基板、一非晶矽薄膜，及一頂電極。Thus, a solar cell of the present invention comprises a substrate, an amorphous germanium film, and a top electrode.
該基板是可導電。The substrate is electrically conductive.
該非晶矽薄膜形成在該透明導電膜上且與該基板為歐姆接觸，包括經過摻雜而有能階差的一P型半導體、一N型半導體，及一能階位於該P、N型半導體的能階之間的本質半導體，該本質半導體具有一結晶區及一非結晶區，該結晶區的比例是佔該本質半導體的25~45%、晶粒尺寸不大於30nm，且位於2070~2100cm-1 之Si-H鍵結強度係佔該結晶區的35~60%，該具有奈米晶矽之非晶矽薄膜可在接收太陽光能時以光伏特效應將光能轉換成電能。The amorphous germanium film is formed on the transparent conductive film and is in ohmic contact with the substrate, and includes a P-type semiconductor doped with energy level difference, an N-type semiconductor, and an energy level located in the P, N-type semiconductor An intrinsic semiconductor between the energy levels, the intrinsic semiconductor having a crystalline region and an amorphous region, the proportion of the crystalline region being 25 to 45% of the intrinsic semiconductor, the grain size being no greater than 30 nm, and located at 2070 to 2100 cm The Si-H bonding strength of -1 accounts for 35-60% of the crystalline region, and the amorphous germanium film with nanocrystalline crystal can convert light energy into electrical energy by the photovoltaic effect when receiving solar energy.
該頂電極，形成在該非晶矽薄膜上，可與該基板相互配合將該非晶矽薄膜產生之電能向外輸出。The top electrode is formed on the amorphous germanium film, and the substrate can cooperate with the substrate to output the electrical energy generated by the amorphous germanium film to the outside.
本發明之功效在於：利用結晶度介於25~45%之間，且控制該成結晶態的晶粒尺寸不大於30nm，並令位於2070~2100cm-1 之Si-H鍵結強度佔該結晶區的35~60%的本質半導體，不僅可減低非晶矽太陽能電池因照光後效率衰減的問題，且能形成多能隙結構，以增加不同波長的光吸收能力，而可增加輸出之光電流。The effect of the invention is that the crystallinity is between 25 and 45%, and the grain size of the crystallized state is controlled to be no more than 30 nm, and the Si-H bonding strength at 2070 to 2100 cm -1 is occupied by the crystal. 35 to 60% of the intrinsic semiconductors in the region can not only reduce the problem of the efficiency of the amorphous silicon solar cell after illumination, but also form a multi-gap structure to increase the light absorption capacity of different wavelengths, and increase the photocurrent of the output. .
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之一個較佳實施例的詳細說明中，將可清楚的呈現。The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.
參閱圖2，本發明太陽能電池之較佳實施例的結構與習知之非晶矽太陽能電池類似，是包含一基板2、一非晶矽薄膜3，及一頂電極4。Referring to FIG. 2, the preferred embodiment of the solar cell of the present invention is similar in structure to the conventional amorphous germanium solar cell, and comprises a substrate 2, an amorphous germanium film 3, and a top electrode 4.
該基板2具有一基材21，及一形成在該基材21表面的透明導電膜22，由於該基材21，及該透明導電膜22的相關製程及材料為本技術領域者所周知，且非為本發明之重點，因此不再多加贅述，於本較佳實施例中，該基材21是玻璃，且該透明導電膜22是由含摻雜載子之氧化鋅為材料所構成，厚度介於50～800nm之間、表面粗糙度介於5~25nm於可見光之穿透率係大於85%且片電阻值係介於5Ω/□至15Ω/□之間。The substrate 2 has a substrate 21 and a transparent conductive film 22 formed on the surface of the substrate 21. The substrate and the related processes and materials of the transparent conductive film 22 are well known in the art. It is not the focus of the present invention, so the description is not repeated. In the preferred embodiment, the substrate 21 is glass, and the transparent conductive film 22 is made of zinc oxide containing doped carriers. The transmittance between 50 and 800 nm and the surface roughness of 5 to 25 nm in visible light is more than 85% and the sheet resistance is between 5 Ω/□ and 15 Ω/□.
值得一提的是，當該透明導電膜22的摻雜載子濃度不足或載子移動率過低時，均會導致導電性能不佳而影響輸出效率，因此，較佳地，該經摻雜的氧化鋅其摻雜載子濃度為1×1019 ~4×1020 cm-3 、結晶尺寸為5~15nm且載子移動率係為5~250cm2 /V-s。It is worth mentioning that when the doping carrier concentration of the transparent conductive film 22 is insufficient or the carrier mobility is too low, the conductivity is poor and the output efficiency is affected. Therefore, preferably, the doping is performed. The zinc oxide has a doping carrier concentration of 1×10 19 to 4×10 20 cm −3 , a crystal size of 5 to 15 nm, and a carrier mobility of 5 to 250 cm 2 /Vs.
參閱表一，表一為在不同比例之O2 :Ar的製程氣體所得到具有不同載子濃度、載子移動率、結晶尺寸及片電阻值的導電膜。Referring to Table 1, Table 1 shows conductive films having different carrier concentrations, carrier mobility, crystal size, and sheet resistance values at different ratios of O 2 :Ar process gases.
該非晶矽薄膜3形成在該透明導電膜22上，表面粗糙度介於2~15nm，且與該透明導電膜22為歐姆接觸，可在接收太陽光能時以光伏特效應將光能轉換成電能，包括經過摻雜而有能階差的一P型半導體31、一N型半導體33，及一能階位於該P、N型半導體31、33的能階之間的本質半導體32。The amorphous germanium film 3 is formed on the transparent conductive film 22 with a surface roughness of 2 to 15 nm and is in ohmic contact with the transparent conductive film 22, and converts light energy into a photovoltaic effect when receiving solar energy. The electric energy includes a P-type semiconductor 31 doped with an energy level difference, an N-type semiconductor 33, and an intrinsic semiconductor 32 having an energy level between the energy levels of the P, N-type semiconductors 31, 33.
特別的是，該本質半導體32具有一結晶區及一非結晶區，該結晶區的比例是佔該本質半導體的25~65%，即該本質半導體32的結晶度是25~65%，且晶粒尺寸不大於30nm。In particular, the intrinsic semiconductor 32 has a crystalline region and an amorphous region, and the ratio of the crystalline region is 25 to 65% of the intrinsic semiconductor, that is, the crystallinity of the intrinsic semiconductor 32 is 25 to 65%, and the crystal The particle size is not more than 30 nm.
要說明的是，由於該本質半導體之結晶區的結晶型態對該本質半導體32的能隙及效率有極大之影響，當結晶區內之結晶愈緻密、缺陷愈少，則量子效率愈佳，而由Si-H鍵結於FT-IR的分析可知，結晶度較為緻密的Si-H鍵會在2070~2100cm-1 之間有較強的吸收而出現峰值，因此，較佳地，該本質半導體32位於2070~2100cm-1 之Si-H鍵結強度係佔該結晶區的35~60%之間。It should be noted that since the crystalline form of the crystalline region of the intrinsic semiconductor has a great influence on the energy gap and efficiency of the intrinsic semiconductor 32, the more dense the crystal in the crystalline region and the less the defects, the better the quantum efficiency. From the analysis of Si-H bond FT-IR, it is known that the Si-H bond with a relatively dense crystallinity has a strong absorption between 2070 and 2100 cm -1 and a peak occurs. Therefore, preferably, the essence The Si-H bonding strength of the semiconductor 32 at 2070-2100 cm -1 is between 35 and 60% of the crystallization region.
特別說明的是，當奈米晶矽之晶粒小於30nm時，可形成量子侷限效應，且可由尺寸調整能隙的變化，當電子受到量子侷限效應的影響，使得原本連續的能帶結構變為***的能階結構，進而使矽原來的間接能隙變為接近直接能隙的能帶結構。此外，量子侷限效應更可藉以改良電特性，以增加可吸收之入射光能譜範圍，但是，當結晶區所佔的比例大於50%時，該本質半導體32的漏電流將隨之提升；反之，當結晶區比例過小，載子移動率亦將隨之下降，因此，較佳地，該結晶區的比例介於25%~50%之間，更佳地，該結晶區的比例介於25%~45%之間。In particular, when the crystal grain of the nanocrystalline crystal is less than 30 nm, a quantum confinement effect can be formed, and the change of the energy gap can be adjusted by the size, and when the electron is affected by the quantum confinement effect, the original continuous band structure becomes The energy level structure of the split, which in turn causes the original indirect energy gap of the crucible to become an energy band structure close to the direct energy gap. In addition, the quantum confinement effect can improve the electrical characteristics to increase the range of absorbable incident light energy spectrum, but when the proportion of the crystallization region is greater than 50%, the leakage current of the intrinsic semiconductor 32 will increase; When the ratio of the crystallization zone is too small, the carrier mobility will also decrease. Therefore, preferably, the ratio of the crystallization zone is between 25% and 50%, and more preferably, the ratio of the crystallization zone is between 25%. Between % and 45%.
藉由控制該本質半導體32的結晶比例是介於25~65%之間且晶粒尺寸不大於30nm，可在本質半導體32引進更多的能帶，形成多能隙結構，以增加不同波長的光吸收，而可增加輸出之光電流。By controlling the crystallization ratio of the intrinsic semiconductor 32 to be between 25 and 65% and the grain size to be no more than 30 nm, more energy bands can be introduced in the intrinsic semiconductor 32 to form a multi-gap structure to increase different wavelengths. Light absorption, which increases the photocurrent of the output.
此外，可再同時於該N型半導體33及P型半導體31導入微晶矽結構，不僅可提升太陽能電池的照光穩定性，且可將本發明太陽能電池的非晶矽薄膜3之高、中、低不同能階中，更進一步形成多能隙、多能帶的結構，可更有效的增加不同波長的光吸收，而可提升輸出之光電流；較佳地，該N型半導體的結晶度是介於50~80%之間，表面粗糙度為2~15nm，且該成結晶態的晶粒尺寸介於10nm~100nm，而其位於2070~2100cm-1 之Si-H鍵結強度係佔結晶比例之45~85%之間，該P型半導體的結晶度是介於10~30%之間，且該成結晶態的晶粒尺寸介於5nm~20nm，而其位於2070~2100cm-1 之Si-H鍵結強度係佔結晶比例之15~35%之間。In addition, the microcrystalline germanium structure can be introduced into the N-type semiconductor 33 and the P-type semiconductor 31 at the same time, which not only improves the illumination stability of the solar cell, but also can increase the height, the medium, and the amorphous germanium film 3 of the solar cell of the present invention. In the low energy level, the structure of the multi-energy gap and the multi-energy band is further formed, and the light absorption of different wavelengths can be more effectively increased, and the photocurrent of the output can be improved; preferably, the crystallinity of the N-type semiconductor is Between 50% and 80%, the surface roughness is 2~15nm, and the grain size of the crystalline state is between 10nm and 100nm, and the Si-H bond strength at 2070~2100cm -1 is crystallized. Between 45 and 85% of the ratio, the crystallinity of the P-type semiconductor is between 10 and 30%, and the crystal grain size of the crystalline state is between 5 nm and 20 nm, and it is located at 2070 to 2100 cm -1 . The Si-H bond strength is between 15 and 35% of the crystallization ratio.
茲將沉積製程壓力為20mtorr，在不同之沉積功率及沉積氣體比例製得之非晶矽半導體膜的表面粗糙度和載子移動率，及本質半導體的結晶度分別整理如表二、表三所示。The deposition process pressure is 20mtorr, and the surface roughness and carrier mobility of the amorphous germanium semiconductor film prepared by different deposition power and deposition gas ratio, and the crystallinity of the intrinsic semiconductor are respectively arranged as shown in Table 2 and Table 3. Show.
於本較佳實施例中，該P型半導體31及該N型半導體33分別是經由III族及V族元素摻雜的P-型非晶矽及N-型非晶矽，該本質半導體32由矽基材料構成，結晶態為奈米晶矽，非結晶態為非晶矽，該N型半導體的結晶度是介於50~80%之間，該成結晶態的晶粒尺寸介於10nm~100nm，而其位於2070~2100cm-1 之Si-H鍵結強度係佔結晶比例之45~85%之間，該P型半導體的結晶度是介於10~30%之間，該成結晶態的晶粒尺寸介於5nm~20nm，而其位於2070~2100cm-1 之Si-H鍵結強度係佔結晶比例之15~35%之間，而可得到能階依序約為1.5~1.8eV、1.3~1.6eV，及1.2~1.4eV的P型半導體31、本質半導體32，及N型本質半導體33之非晶矽薄膜3結構。In the preferred embodiment, the P-type semiconductor 31 and the N-type semiconductor 33 are respectively P-type amorphous germanium and N-type amorphous germanium doped by group III and group V elements, and the intrinsic semiconductor 32 is composed of The base material is composed of a crystalline state of nanocrystalline germanium and an amorphous state of amorphous germanium. The crystallinity of the N-type semiconductor is between 50 and 80%, and the crystallite size of the crystalline state is between 10 nm and ~ 100 nm, and its Si-H bonding strength at 2070-2100 cm -1 is between 45 and 85% of the crystallization ratio, and the crystallinity of the P-type semiconductor is between 10 and 30%. The grain size is between 5 nm and 20 nm, and the Si-H bond strength at 2070~2100 cm -1 is between 15 and 35% of the crystallization ratio, and the order of energy is about 1.5 to 1.8 eV. The structure of the amorphous germanium film 3 of the P-type semiconductor 31, the intrinsic semiconductor 32, and the N-type intrinsic semiconductor 33 of 1.3 to 1.6 eV and 1.2 to 1.4 eV.
該頂電極4，形成在該非晶矽薄膜3上，可與該透明導電膜22相互配合將該非晶矽薄膜3產生之電能向外輸出，於本較佳實施例中，該頂電極4是選自鋁且具有2~15nm的表面粗糙度。The top electrode 4 is formed on the amorphous germanium film 3, and the transparent conductive film 22 can cooperate with the transparent conductive film 22 to output the electric energy generated by the amorphous germanium film 3. In the preferred embodiment, the top electrode 4 is selected. It is self-aluminum and has a surface roughness of 2 to 15 nm.
本發明該本質半導體32的奈米晶矽是位於該非晶矽之中，而由於奈米晶矽具有比非晶矽更佳的導電性-奈米晶矽之載子遷移率(Carrier mobility)比一般非晶矽薄膜高出1~2個數量級，而暗電導值則介於10-5 ~10-7 (S.cm-1 )之 間，較一般非晶矽高出3~4個數量級，同時，奈米晶矽具有比非晶矽更佳的光吸收特性與照光穩定性，因此可防止非晶矽之缺陷結構中電子、電洞的複合，而可提升太陽能電池的開路(open circuit)電壓，提高非晶矽太陽電池的轉換效率，同時也可減低非晶矽結構中大量的缺陷以及未鍵結的矽懸鍵，在強烈的光線照射下，電池效率衰減的問題，而可提升太陽能電池的使用壽命。The nanocrystalline germanium of the intrinsic semiconductor 32 of the present invention is located in the amorphous germanium, and since the nanocrystalline germanium has better conductivity than the amorphous germanium - the carrier mobility ratio of the nanocrystalline germanium Generally, the amorphous germanium film is one to two orders of magnitude higher, and the dark conductance value is between 10 -5 and 10 -7 (S.cm -1 ), which is 3-4 orders of magnitude higher than the general amorphous germanium. At the same time, the nanocrystalline germanium has better light absorption characteristics and illumination stability than the amorphous germanium, thereby preventing the recombination of electrons and holes in the defect structure of the amorphous germanium, and improving the open circuit of the solar cell. The voltage increases the conversion efficiency of the amorphous germanium solar cell, and also reduces a large number of defects in the amorphous germanium structure and the unbonded anchoring button, which can attenuate the battery efficiency under strong light irradiation, and can improve solar energy. Battery life.
參閱圖3、圖4，圖3所示為射頻功率密度為0.55W/cm2 ，在不同氫氣稀釋比值R(R=H2 /SiH4 )，所製得之本質半導體的拉曼頻譜圖，圖4則為R=30、射頻功率1200W，及沉積壓力為30mtorr的條件下製得之本質半導體的FT-IR分析圖譜。Referring to FIG. 3 and FIG. 4, FIG. 3 shows a Raman spectrum diagram of an intrinsic semiconductor prepared by diluting a ratio R (R=H 2 /SiH 4 ) at a hydrogen power density of 0.55 W/cm 2 . Figure 4 shows the FT-IR analysis of an intrinsic semiconductor prepared with R = 30, RF power of 1200 W, and a deposition pressure of 30 mtorr.
由圖3可知在R=10、R=20、R=30之峰值都介於480cm-1 左右。在R=40時，圖中開始出現510~520 cm-1 之峰值，對照其結晶度，可發現當氫稀釋比逐漸提高至R=40時，結晶度會緩慢上升，其中，R=H2 /SiH4 。As can be seen from Fig. 3, the peaks at R = 10, R = 20, and R = 30 are all around 480 cm -1 . When R=40, the peak of 510~520 cm -1 begins to appear in the figure. Compared with the crystallinity, it can be found that when the hydrogen dilution ratio is gradually increased to R=40, the crystallinity will rise slowly, where R=H 2 /SiH 4 .
參閱圖4，圖4中曲線1為該本質半導體的FT-IR圖譜，曲線2和曲線3為該本質半導體的結晶區，曲線4和曲線5則為該本質半導體的非結晶區，曲線4的吸收峰值代表的是非晶矽(a-Si：H)的Si-H鍵結，曲線5的吸收峰值則為該本質半導體於沉積過程中之矽甲烷(SiH4 )因為解離不完全或於反應過程中形成之團聚物(SiH3 )的Si-H鍵結，而吸收峰值位於2070~2100cm-1 之間的曲線2代表的則是該結晶區中較為緻密且缺陷較少的微晶矽和奈米晶矽的Si-H鍵 結，曲線3的吸收峰值則表示該結晶區中結晶結構較為鬆散且缺陷較多的Si-H鍵結，而由各區的Si-H光譜分析結果可知，本實施例位於2070~2100cm-1 之間的Si-H鍵結約佔該為56%。Referring to FIG. 4, curve 1 in FIG. 4 is an FT-IR spectrum of the intrinsic semiconductor, curves 2 and 3 are crystal regions of the intrinsic semiconductor, and curves 4 and 5 are amorphous regions of the intrinsic semiconductor, and curve 4 is The absorption peak represents the Si-H bond of amorphous yttrium (a-Si:H), and the absorption peak of curve 5 is the methane (SiH 4 ) of the intrinsic semiconductor during the deposition process because the dissociation is incomplete or in the reaction process. The Si-H bond of the agglomerate (SiH 3 ) formed in the middle, and the curve 2 with the absorption peak between 2070 and 2100 cm -1 represents the denser and less defective microcrystalline germanium and naphthalene in the crystalline region. The Si-H bond of the rice bismuth, the absorption peak of the curve 3 indicates the Si-H bond in which the crystal structure is loose and has many defects, and the Si-H spectrum analysis results of each region show that The Si-H bond of the embodiment between 2070 and 2100 cm -1 accounts for about 56%.
綜上所述，本發明藉由分別或同時控制該本質半導體、N型半導體及P型半導體之結晶度及該呈結晶態之晶粒尺寸，不僅可提升太陽能電池的照光穩定性，且可將太陽能電池的非晶矽薄膜之高、中、低不同能階中，更進一步形成多能隙、多能帶的結構，可更有效的增加不同波長的光吸收，而可提升輸出之光電流，確實可達到本發明之目的。In summary, the present invention can not only improve the crystal stability of the solar cell, but also improve the crystal stability of the solar cell by separately or simultaneously controlling the crystallinity of the intrinsic semiconductor, the N-type semiconductor, and the P-type semiconductor. In the high, medium and low energy levels of the amorphous germanium film of the solar cell, a multi-energy gap and multi-energy band structure is further formed, which can more effectively increase the light absorption of different wavelengths, and can improve the output photocurrent. The object of the invention can indeed be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
2‧‧‧基板2‧‧‧Substrate
21‧‧‧基材21‧‧‧Substrate
22‧‧‧透明導電膜22‧‧‧Transparent conductive film
3‧‧‧非晶矽薄膜3‧‧‧Amorphous film
31‧‧‧P型半導體31‧‧‧P-type semiconductor
32‧‧‧本質半導體32‧‧‧ Essential Semiconductor
33‧‧‧N型半導體33‧‧‧N type semiconductor
4‧‧‧頂電極4‧‧‧ top electrode
圖1是一示意圖，說明習知非晶矽薄膜太陽能電池結構；圖2是一示意圖，說明本發明太陽能電池之一較佳實施例；圖3是一拉曼頻譜圖，說明本發明該較佳實施例之本質半導體；及圖4是一FT-IR光譜圖，說明本發明該較佳實施例之本質半導體不同Si-H鍵結的吸收峰值。1 is a schematic view showing a conventional amorphous germanium thin film solar cell structure; FIG. 2 is a schematic view showing a preferred embodiment of the solar cell of the present invention; and FIG. 3 is a Raman spectrogram showing the preferred embodiment of the present invention. The intrinsic semiconductor of the embodiment; and Figure 4 is an FT-IR spectrum showing the absorption peaks of different Si-H bonds of the intrinsic semiconductor of the preferred embodiment of the invention.
2．．．基板2. . . Substrate
21．．．基材twenty one. . . Substrate
22．．．透明導電膜twenty two. . . Transparent conductive film
3．．．非晶矽薄膜3. . . Amorphous germanium film
31．．．P型半導體31. . . P-type semiconductor
32．．．本質半導體32. . . Essential semiconductor
33．．．N型半導體33. . . N-type semiconductor
4．．．頂電極4. . . Top electrode
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98146346A TWI401812B (en) | 2009-12-31 | 2009-12-31 | Solar battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98146346A TWI401812B (en) | 2009-12-31 | 2009-12-31 | Solar battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201123486A TW201123486A (en) | 2011-07-01 |
| TWI401812B true TWI401812B (en) | 2013-07-11 |
Family
ID=45046697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW98146346A TWI401812B (en) | 2009-12-31 | 2009-12-31 | Solar battery |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI401812B (en) |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US200A (en) * | 1837-05-22 | Geoege | ||
| US4672148A (en) * | 1984-12-05 | 1987-06-09 | Sharp Kabushiki Kaisha | Thin-film solar cells |
| US5288338A (en) * | 1990-05-23 | 1994-02-22 | Mitsubishi Denki Kabushiki Kaisha | Solar cell and method of producing the solar cell |
| US5336623A (en) * | 1992-03-02 | 1994-08-09 | Showa Shell Sekiyu K.K. | Process for producing integrated solar cell |
| US5456763A (en) * | 1994-03-29 | 1995-10-10 | The Regents Of The University Of California | Solar cells utilizing pulsed-energy crystallized microcrystalline/polycrystalline silicon |
| US5538564A (en) * | 1994-03-18 | 1996-07-23 | Regents Of The University Of California | Three dimensional amorphous silicon/microcrystalline silicon solar cells |
| US5677236A (en) * | 1995-02-24 | 1997-10-14 | Mitsui Toatsu Chemicals, Inc. | Process for forming a thin microcrystalline silicon semiconductor film |
| US6121541A (en) * | 1997-07-28 | 2000-09-19 | Bp Solarex | Monolithic multi-junction solar cells with amorphous silicon and CIS and their alloys |
| US6166319A (en) * | 1997-08-01 | 2000-12-26 | Canon Kabushiki Kaisha | Multi-junction photovoltaic device with microcrystalline I-layer |
| US6218702B1 (en) * | 1995-12-09 | 2001-04-17 | Semiconductor Energy Laboratory, Co. Ltd. | Microcrystal silicon film and its manufacturing method, and photoelectric conversion device and its manufacturing method |
| TW200810138A (en) * | 2006-06-23 | 2008-02-16 | Applied Materials Inc | Methods and apparatus for depositing a microcrystalline silicon film for photovoltaic device |
| TWM335796U (en) * | 2008-02-01 | 2008-07-01 | Contrel Technology Co Ltd | A silicon-based thin film solar-cell with multijunction |
| TW200834672A (en) * | 2007-02-02 | 2008-08-16 | Ind Tech Res Inst | Method of forming microcrystalline silicon film |
| TW200910621A (en) * | 2007-06-21 | 2009-03-01 | Jusung Eng Co Ltd | Solar cell, method of fabricating the same and apparatus for fabricating the same |
| TW200917513A (en) * | 2007-08-28 | 2009-04-16 | Jusung Eng Co Ltd | Method of fabricating solar cell using microwave and apparatus for the same |
| US20090104733A1 (en) * | 2007-10-22 | 2009-04-23 | Yong Kee Chae | Microcrystalline silicon deposition for thin film solar applications |
| TW200924202A (en) * | 2007-11-30 | 2009-06-01 | Delta Electronics Inc | Solar cell and manufacturing method thereof |
| TW200924067A (en) * | 2007-08-08 | 2009-06-01 | Ramesh Kakkad | Methods of fabricating crystalline silicon, thin film transistors, and solar cells |
| TW200933917A (en) * | 2007-11-02 | 2009-08-01 | Applied Materials Inc | Plasma treatment between deposition processes |
| TW200950114A (en) * | 2008-05-27 | 2009-12-01 | Kisco Corp | Tandem thin-film silicon solar cell and method for manufacturing the same |
| TW200952192A (en) * | 2008-05-30 | 2009-12-16 | Semiconductor Energy Lab | Photoelectric conversion device and method for manufacturing the same |
-
2009
- 2009-12-31 TW TW98146346A patent/TWI401812B/en active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US200A (en) * | 1837-05-22 | Geoege | ||
| US4672148A (en) * | 1984-12-05 | 1987-06-09 | Sharp Kabushiki Kaisha | Thin-film solar cells |
| US5288338A (en) * | 1990-05-23 | 1994-02-22 | Mitsubishi Denki Kabushiki Kaisha | Solar cell and method of producing the solar cell |
| US5336623A (en) * | 1992-03-02 | 1994-08-09 | Showa Shell Sekiyu K.K. | Process for producing integrated solar cell |
| US5538564A (en) * | 1994-03-18 | 1996-07-23 | Regents Of The University Of California | Three dimensional amorphous silicon/microcrystalline silicon solar cells |
| US5456763A (en) * | 1994-03-29 | 1995-10-10 | The Regents Of The University Of California | Solar cells utilizing pulsed-energy crystallized microcrystalline/polycrystalline silicon |
| US5677236A (en) * | 1995-02-24 | 1997-10-14 | Mitsui Toatsu Chemicals, Inc. | Process for forming a thin microcrystalline silicon semiconductor film |
| US6218702B1 (en) * | 1995-12-09 | 2001-04-17 | Semiconductor Energy Laboratory, Co. Ltd. | Microcrystal silicon film and its manufacturing method, and photoelectric conversion device and its manufacturing method |
| US6368892B1 (en) * | 1997-07-28 | 2002-04-09 | Bp Corporation North America Inc. | Monolithic multi-junction solar cells with amorphous silicon and CIS and their alloys |
| US6121541A (en) * | 1997-07-28 | 2000-09-19 | Bp Solarex | Monolithic multi-junction solar cells with amorphous silicon and CIS and their alloys |
| US6166319A (en) * | 1997-08-01 | 2000-12-26 | Canon Kabushiki Kaisha | Multi-junction photovoltaic device with microcrystalline I-layer |
| TW200810138A (en) * | 2006-06-23 | 2008-02-16 | Applied Materials Inc | Methods and apparatus for depositing a microcrystalline silicon film for photovoltaic device |
| TW200834672A (en) * | 2007-02-02 | 2008-08-16 | Ind Tech Res Inst | Method of forming microcrystalline silicon film |
| TW200910621A (en) * | 2007-06-21 | 2009-03-01 | Jusung Eng Co Ltd | Solar cell, method of fabricating the same and apparatus for fabricating the same |
| TW200924067A (en) * | 2007-08-08 | 2009-06-01 | Ramesh Kakkad | Methods of fabricating crystalline silicon, thin film transistors, and solar cells |
| TW200917513A (en) * | 2007-08-28 | 2009-04-16 | Jusung Eng Co Ltd | Method of fabricating solar cell using microwave and apparatus for the same |
| US20090104733A1 (en) * | 2007-10-22 | 2009-04-23 | Yong Kee Chae | Microcrystalline silicon deposition for thin film solar applications |
| TW200933917A (en) * | 2007-11-02 | 2009-08-01 | Applied Materials Inc | Plasma treatment between deposition processes |
| TW200924202A (en) * | 2007-11-30 | 2009-06-01 | Delta Electronics Inc | Solar cell and manufacturing method thereof |
| TWM335796U (en) * | 2008-02-01 | 2008-07-01 | Contrel Technology Co Ltd | A silicon-based thin film solar-cell with multijunction |
| TW200950114A (en) * | 2008-05-27 | 2009-12-01 | Kisco Corp | Tandem thin-film silicon solar cell and method for manufacturing the same |
| TW200952192A (en) * | 2008-05-30 | 2009-12-16 | Semiconductor Energy Lab | Photoelectric conversion device and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201123486A (en) | 2011-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5285651B2 (en) | Manufacturing method of solar cell | |
| US20050092357A1 (en) | Hybrid window layer for photovoltaic cells | |
| JP2006080557A (en) | Improved stabilizing properties of amorphous silicon series element manufactured by high hydrogen dilution low temperature plasma vapor deposition | |
| JP2001267611A (en) | Thin-film solar battery and its manufacturing method | |
| US8679892B2 (en) | Method for manufacturing silicon thin-film solar cells | |
| JPH0738454B2 (en) | Solar cell | |
| JP2009517876A (en) | Photocell | |
| JPH06151916A (en) | Multijunction photoelectric device and its manufacture | |
| KR20130028449A (en) | Thin film type solar cells and manufacturing method thereof | |
| JP2012520563A (en) | Solar cell | |
| EP2599127B1 (en) | Multiple-junction photoelectric device and its production process | |
| JP4864077B2 (en) | Photoelectric conversion device and manufacturing method thereof | |
| JP2008283075A (en) | Manufacturing method of photoelectric conversion device | |
| JP6047494B2 (en) | Thin film photoelectric conversion device and manufacturing method thereof | |
| US7122736B2 (en) | Method and apparatus for fabricating a thin-film solar cell utilizing a hot wire chemical vapor deposition technique | |
| WO2021010127A1 (en) | Semiconductor device and solar battery and production method for semiconductor device | |
| TWI401812B (en) | Solar battery | |
| Yan et al. | High efficiency amorphous and nanocrystalline silicon thin film solar cells on flexible substrates | |
| JP2005159320A (en) | Solar cell and manufacturing method for the same | |
| TWI483405B (en) | Photovoltaic cell and method of manufacturing a photovoltaic cell | |
| JP2009076742A (en) | Photovoltaic element, and manufacturing method thereof | |
| WO2013031906A1 (en) | Photoelectric conversion device and method for manufacturing same | |
| JP4441298B2 (en) | Photoelectric conversion device and manufacturing method thereof | |
| WO2011033072A2 (en) | High-efficiency amorphous silicon photovoltaic devices | |
| JP2003258286A (en) | Thin film solar battery and manufacturing method thereof |