TWI535875B - Preparation method of magnesia - zinc sputtering target doped with group IIIA elements - Google Patents
Preparation method of magnesia - zinc sputtering target doped with group IIIA elements Download PDFInfo
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本發明係有關一種濺鍍靶材之製備方法，特別是關於一種摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材之製備方法。The invention relates to a method for preparing a sputtering target, in particular to a method for preparing a magnesium oxide zinc sputtering target doped with a group IIIA element.
透明導電薄膜是指可被可見光穿透，且具有良好導電性的薄膜。透明導電薄膜的種類有金屬薄膜、金屬氧化物薄膜、金屬氮化物薄膜及有機導電高分子薄膜等數種，但在目前在工業上使用的主流透明導電薄膜材料，仍為金屬透明導電氧化物(transparent conductive oxide,TCO)薄膜。由於TCO薄膜具有極佳的導電特性，電阻率(resistivity)可低至2×10-4歐姆-公分(Ω-cm)以下，約為最佳導電銀金屬之100倍]、高可見光穿透性及高紅外光之反射性，為平面顯示器、觸控面板及太陽能面板等光電裝置中所使用的透明導電電極的最重要材料。為獲得可見光區的透明性，TCO材料通常採用能隙寬度大於可見光能量的半導體金屬氧化物，並在半導體金屬氧化物材料中摻雜雜質增加導電性，例如：在氧化銦中加入少量錫形成氧化銦錫薄膜(ITO)，或在氧化鋅中摻雜鋁的氧化鋁鋅薄膜(AZO)；而TCO薄膜的導電特性除受製程方法及製程條件的影響外，摻雜雜質的比例更是影響TCO薄膜導電特性的關鍵因素。A transparent conductive film refers to a film that can be penetrated by visible light and has good electrical conductivity. The types of transparent conductive films are metal thin films, metal oxide thin films, metal nitride thin films, and organic conductive polymer thin films, but the mainstream transparent conductive thin film materials currently used in the industry are still metal transparent conductive oxides ( Transparent conductive oxide (TCO) film. Since the TCO film has excellent electrical conductivity, the resistivity can be as low as 2 × 10 -4 ohm-cm (Ω-cm), which is about 100 times that of the best conductive silver metal], and high visible light transmittance. And high-infrared light reflectivity, the most important material for transparent conductive electrodes used in optoelectronic devices such as flat panel displays, touch panels and solar panels. In order to obtain the transparency of the visible light region, the TCO material usually adopts a semiconductor metal oxide having a gap width larger than the visible light energy, and doping impurities in the semiconductor metal oxide material increases conductivity, for example, adding a small amount of tin to the indium oxide to form oxidation. Indium tin film (ITO), or aluminum-zinc oxide film (AZO) doped with zinc oxide; the conductivity of TCO film is affected by the process method and process conditions, and the proportion of doping impurities affects TCO. A key factor in the conductive properties of thin films.
目前在銅銦鎵硒(CuInGaSe2,CIGS)太陽能電池元件中，所使用作為上電極(front electrode)以及窗層(window layer)薄膜材料之TCO薄膜為AZO薄膜。AZO薄膜不僅具有低電阻率及高可見光穿透度等優點，其價格便宜且原料易取得，是CIGS太陽能元件之TCO上電極與窗層材料的首選，在工業上也已經被大量使用。Currently, in a copper indium gallium selenide (CuInGaSe 2 , CIGS) solar cell element, a TCO film used as a front electrode and a window layer film material is an AZO film. AZO film not only has the advantages of low resistivity and high visible light transmittance, but also is cheap and easy to obtain raw materials. It is the first choice for TCO upper electrode and window layer materials of CIGS solar components, and has been widely used in industry.
AZO薄膜的能隙約為3.31-3.51電子伏特(ev)，在可見光區範圍下，其穿透度可達90%以上，且電阻率可低至2.7×10-4Ω-cm。如第1圖所示，Ishizuka等人在2005年，製備利用AZO薄膜10當作上電極及窗層材料，搭配本質氧化鋅(intrinsic zinc oxide,i-ZnO)層12和硫化鎘(cadmium sulfide,CdS)層14當作緩衝層之CIGS太陽能電池模組，其光電轉換效率約為16%。The AZO film has an energy gap of about 3.31-3.51 electron volts (ev), and its transmittance is over 90% in the visible region, and the resistivity can be as low as 2.7 × 10 -4 Ω-cm. As shown in Fig. 1, Ishizuka et al. in 2005 prepared AZO film 10 as the upper electrode and window layer material, together with intrinsic zinc oxide (i-ZnO) layer 12 and cadmium sulfide (cadmium sulfide, The CdS) layer 14 acts as a buffer layer for the CIGS solar cell module, and its photoelectric conversion efficiency is about 16%.
由文獻中可以知道，使用AZO薄膜10當作上電極及窗層材料，雖然可見光的穿透率高，但在近紅外光的波長範圍內，AZO薄膜卻會反射在太陽光譜中之近紅外光，且會隨著AZO薄膜電阻係數的下降而產生更高的反射率，如第2圖及第3圖所示。此一現象便會造成使用AZO為上電極與窗層材料的CIGS太陽能元件之整體太陽光穿透率不佳，使得CIGS太陽能元件之光電轉換效能降低，並會因為無法利用近紅外光波長而造成能源效率無法有效提高。此外，在工業上，AZO薄膜係由AZO濺鍍靶材採用濺鍍法所形成，由於靶材表面緻密度不夠，因此常有微粒(nodules)生成，此生成會在濺鍍過程中，導致AZO薄膜品質降低。若為了去除微粒生成，工廠的生產成本還會因此而提高。It can be known from the literature that the AZO film 10 is used as the upper electrode and the window layer material. Although the transmittance of visible light is high, the AZO film reflects the near-infrared light in the solar spectrum in the wavelength range of the near-infrared light. And will have higher reflectivity as the resistivity of the AZO film decreases, as shown in Figures 2 and 3. This phenomenon will result in poor overall solar transmittance of CIGS solar components using AZO as the upper electrode and the window layer material, which will reduce the photoelectric conversion efficiency of CIGS solar components, and will result in the inability to utilize the near-infrared wavelength. Energy efficiency cannot be effectively improved. In addition, in the industry, AZO thin films are formed by sputtering of AZO sputtering targets. Due to the insufficient density of the surface of the target, there are often nodules, which will cause AZO during the sputtering process. The film quality is reduced. If the particle generation is removed, the production cost of the plant will increase.
而在現行之CIGS太陽能元件中，CdS已是一個廣被使用的緩衝層物質，但因為鎘為劇毒物質會對環境造成衝擊，更有後續回收處理的問題。為了解決這個問題，文獻上報導可以利用氧化鎂鋅(magnesium zinc oxide,MZO)當做CIGS太陽能元件中緩衝層，來替代目前所使用之CdS。由於MZO的晶體結構，是以AZO相同的氧化鋅纖鋅礦結構為主，且電阻率較大，因此在使用MZO作為緩衝層的CIGS太陽能元件中，若仍以AZO薄膜作為上電極及窗層材料，由於AZO在結構上與MZO緩衝層的結構相近，加上元件結構上不須另鍍一層i-ZnO來降低電子-電洞再結合的問題，是可以同時降低結構與製程的複雜性及膜層間晶格不匹配的效應。但即便AZO在晶格匹配及結構與製程簡化上，有潛力在新一世代使用MZO為緩衝層的CIGS太陽能元件中使用，但上述在近紅外光區穿透率不佳，及與新緩衝層MZO材料在晶格結構及整體光學性質搭配上可能產生的問題，都是未來必須面對及探討的問題。Among the current CIGS solar components, CdS is already a widely used buffer layer material, but because cadmium is a highly toxic substance, it will have an impact on the environment, and there is a problem of subsequent recycling. In order to solve this problem, it has been reported in the literature that magnesium zinc oxide (MZO) can be used as a buffer layer in CIGS solar elements instead of the currently used CdS. Since the crystal structure of MZO is mainly composed of the same zinc oxide wurtzite structure of AZO and the resistivity is large, in the CIGS solar element using MZO as the buffer layer, the AZO film is still used as the upper electrode and the window layer. The material, because AZO is similar in structure to the structure of the MZO buffer layer, and the component structure does not need to be further coated with i-ZnO to reduce the electron-hole recombination problem, which can simultaneously reduce the complexity of the structure and process. The effect of lattice mismatch between layers. However, even though AZO has a potential for lattice matching and structure and process simplification, it has the potential to be used in CIGS solar components using MZO as a buffer layer in the new generation, but the above-mentioned penetration in the near-infrared region is not good, and with the new buffer layer. The problems that may occur in the lattice structure and overall optical properties of MZO materials are issues that must be faced and discussed in the future.
目前業界所用之主流TCO材料為氧化銦錫(indium tin oxide,ITO)，成分組成為重量百分比之90%In2O3和10%的SnO2，屬於寬能隙物質，導電特性為n型，薄膜的電阻率約在1.5~3×10-4Ω-cm，在可見光及近紅外光波長範圍具有高穿透度，具備使用在CIGS太陽能電池模組上，作為上電極以及窗層材料的潛力。2003年Satoh等人以ITO當作TCO窗層物質搭配CdS緩衝層，再搭配其他膜層之後，所得的CIGS太陽能電池元件的光電轉換效率約有10-13%，而其中的ITO厚度和CdS的厚度都約在0.1微米(μm)左右。但ITO目前已被大量使用在顯示面板及觸控面板上，隨著平面顯示器及使用觸控介面之智慧裝置之普及化，其用量及需求量急遽攀升，且因為銦金屬的含量稀少的稀有金屬，在原料取得來源易受到限制且成本昂貴。除此之外，ITO本身的結構屬體心(bixbyite)的立方體結構，不適合在以MZO緩衝層的CIGS太陽能元件中使用。因此，ITO較AZO更不適合在新一世代使用MZO為緩衝層的CIGS太陽能元件中，作為太陽能電池元件之TCO上電極及窗層材料。At present, the mainstream TCO material used in the industry is indium tin oxide (ITO), which is composed of 90% by weight of In 2 O 3 and 10% of SnO 2 , which is a wide band gap material and has an electric conductivity of n type. The resistivity of the film is about 1.5~3×10 -4 Ω-cm, and it has high transmittance in the visible and near-infrared wavelength range. It has the potential to be used as a top electrode and window layer material on CIGS solar cell modules. . In 2003, Satoh et al. used ITO as a TCO window layer material with a CdS buffer layer, and after matching other layers, the photoelectric conversion efficiency of the obtained CIGS solar cell element was about 10-13%, and the ITO thickness and CdS therein. The thickness is about 0.1 micrometer (μm). However, ITO has been widely used in display panels and touch panels. With the popularization of flat-panel displays and smart devices using touch interfaces, the amount and demand are rising rapidly, and rare metals with indium metal content are scarce. The source of raw materials is easily limited and expensive. In addition, the structure of ITO itself is a bixbyite cubic structure, which is not suitable for use in CIGS solar elements with MZO buffer layers. Therefore, ITO is less suitable than AZO for the TCO upper electrode and window layer material of the solar cell element in the CIGS solar element using MZO as the buffer layer in the new generation.
由以上述可知，做為CIGS太陽能電池之上電極與窗層的TCO材料，除了必須保留TCO薄膜的特性，即為可見光透光性好且導電性佳外，尚須配合緩衝層材料之選擇，並需要增加其近紅外光穿透度，而材料之成本、供應量及來源更是需要考量的因素。所以，找尋可替代AZO的TCO材料，來作為CIGS太陽能元件之上電極與窗層材料，是在CIGS太陽能元件的發展上一個相當重要的課題。It can be seen from the above that as the TCO material of the upper electrode and the window layer of the CIGS solar cell, in addition to the characteristics of the TCO film, that is, the visible light transmittance is good and the conductivity is good, the selection of the buffer layer material is required. It is necessary to increase its near-infrared light penetration, and the cost, supply and source of the material are factors that need to be considered. Therefore, looking for a TCO material that can replace AZO as a material for the upper electrode and window layer of CIGS solar components is a very important issue in the development of CIGS solar components.
因此，本發明係在針對上述之困擾，提出一種摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材之製備方法，以解決習知所產生的問題。Therefore, the present invention has been made in view of the above problems, and proposes a method for preparing a magnesium oxide zinc sputtering target doped with a Group IIIA element to solve the problems caused by the prior art.
本發明之主要目的，在於提供一種摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材之製備方法，其製備出的濺鍍靶材，具有高緻密度與低電阻率，可作為磁控濺鍍使用的靶材，且其於銅銦鎵硒(CuInGaSe2,CIGS)太陽能電池上所形成之上電極及窗層材料，不但與作為緩衝層之氧化鎂鋅層之晶體結構相近，以減少晶格不匹配之問題，同時亦具有紅外光之高穿透性，以提高整體太陽光穿透率。The main object of the present invention is to provide a method for preparing a magnesium oxide zinc sputtering target doped with a group IIIA element, which has a sputtering target having high density and low electrical resistivity and can be used as magnetron sputtering. The target used, and the upper electrode and the window layer material formed on the copper indium gallium selenide (CuInGaSe 2 , CIGS) solar cell are similar to the crystal structure of the magnesium zinc oxide layer as the buffer layer to reduce the lattice The problem of mismatching also has the high penetration of infrared light to improve the overall solar transmittance.
為達上述目的，本發明提供一種摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材之製備方法，首先提供一含有氧化鎂鋅與ⅢA族元素之氧化鎂鋅混合物，接著加水或乙醇以研磨氧化鎂鋅混合物，以混合為氧化鎂鋅合成漿料。繼續，乾燥氧化鎂鋅混合漿料，再將其以固態反應法在高溫反應，以得到氧化鎂鋅合成粉末。加入黏著劑於氧化鎂鋅合成粉末上，並進行研磨混合以進行造粒，得到氧化鎂鋅合成造粒粉末。下一步驟係對氧化鎂鋅合成造粒粉末以篩網過篩，以得到氧化鎂鋅合成篩選粉末。篩選完後，則對氧化鎂鋅合成篩選粉末進行胚化處理，以得到氧化鎂鋅合成生胚，最後將氧化鎂鋅合成生胚放入高溫爐中，並通入惰性氣體進行高溫燒結，以得到摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材。In order to achieve the above object, the present invention provides a method for preparing a magnesium oxide zinc sputtering target doped with a group IIIA element, firstly providing a magnesium magnesium oxide mixture containing zinc oxide and a group IIIA element, followed by adding water or ethanol for grinding oxidation. A mixture of magnesium and zinc is mixed into a slurry of magnesium oxide and zinc. Continuing, the magnesium magnesium oxide mixed slurry is dried, and then reacted at a high temperature by a solid state reaction method to obtain a magnesium zinc oxide synthetic powder. An adhesive is added to the magnesium magnesium oxide synthetic powder, and ground and mixed for granulation to obtain a magnesia-zinc synthetic granulated powder. The next step is to sieve the magnesium oxide zinc synthetic granulated powder through a sieve to obtain a magnesium oxide zinc synthetic screening powder. After screening, the magnesium oxide zinc synthetic screening powder is subjected to embryonic treatment to obtain magnesium oxide zinc to synthesize raw embryos, and finally the magnesium oxide zinc synthetic raw embryos are placed in a high temperature furnace, and an inert gas is introduced for high temperature sintering. A magnesium oxide zinc sputtering target doped with a Group IIIA element is obtained.
茲為使 貴審查委員對本發明之結構特徵及所達成之功效更有進一步之瞭解與認識，謹佐以較佳之實施例圖及配合詳細之說明，說明如後：For a better understanding and understanding of the structural features and the achievable effects of the present invention, please refer to the preferred embodiment and the detailed description.
以下即介紹製作濺鍍靶材之流程，請參閱第4圖。首先如步驟S10所示，提供一含有氧化鎂鋅與ⅢA族元素之氧化鎂鋅混合物，其中ⅢA族元素佔0.5～10重量百分比(wt%)，氧化鎂佔0.5～30wt%，氧化鋅則佔其餘比例。此含ⅢA族元素之氧化鎂鋅混合物有兩種形成方式，其一，係將佔有0.5～10 wt%的ⅢA族元素之氧化物加入佔其餘重量百分比氧化鎂鋅粉末中以形成之；其二，則為將佔有0.5- 10wt%的ⅢA族元素之氧化物，加入佔有0.5-30 wt%之氧化鎂及佔其餘重量百分比的氧化鋅中以形成之。此外，ⅢA族元素之選擇可為鋁(Al)、鎵(Ga)、銦(In)。接著，如步驟S12所示，將含ⅢA族元素之氧化鎂鋅混合物置入球磨罐中加水或乙醇研磨，以均勻混合為含ⅢA族元素之一氧化鎂鋅混合漿料，且混合時間可介於16至24小時。再來，如步驟S14所示，將氧化鎂鋅混合漿料置入烘箱中進行乾燥，且乾燥溫度設定在攝氏20至80度，再將乾燥後之氧化鎂鋅混合漿料以固態反應法在600-850℃反應2-6小時，以得到含ⅢA族元素之氧化鎂鋅合成粉末。The procedure for making a sputter target is described below, see Figure 4. First, as shown in step S10, a zinc-magnesium-zinc mixture containing zinc oxide and a group IIIA element is provided, wherein the group IIIA element accounts for 0.5 to 10% by weight (wt%), the magnesium oxide accounts for 0.5 to 30% by weight, and the zinc oxide accounts for The remaining proportion. The zinc-magnesium-zinc mixture containing the group IIIA element has two forms of formation, one of which is formed by adding 0.5 to 10 wt% of the oxide of the group IIIA element to the remaining weight percentage of the magnesia-zinc powder to form the second; The oxide of the group IIIA element, which is occupied by 0.5 to 10% by weight, is added to the zinc oxide which accounts for 0.5-30% by weight and the remaining weight percentage of zinc oxide. Further, the Group IIIA element may be selected from aluminum (Al), gallium (Ga), and indium (In). Next, as shown in step S12, the magnesium-magnesium-zinc mixture containing the group IIIA element is placed in a ball mill tank and added with water or ethanol to be uniformly mixed into a magnesium-zinc-zinc mixed slurry containing one of the group IIIA elements, and the mixing time can be From 16 to 24 hours. Then, as shown in step S14, the magnesium-zinc-zinc mixed slurry is placed in an oven for drying, and the drying temperature is set at 20 to 80 degrees Celsius, and then the dried magnesium-zinc-zinc mixed slurry is solid-state reaction method. The reaction is carried out at 600-850 ° C for 2-6 hours to obtain a magnesium oxide zinc synthetic powder containing a Group IIIA element.
下一步驟係如步驟S16所示，將氧化鎂鋅合成粉末加入作為黏著劑之聚乙烯醇(PVA)，進行研磨混合後造粒，以增加粉末流動性，而得到氧化鎂鋅合成造粒粉末。在得到造粒粉末後，如步驟S18所示，以篩網對氧化鎂鋅合成造粒粉末進行過篩，以得到氧化鎂鋅合成篩選粉末，其中篩網之大小為100～600篩孔(mesh)。然後，如步驟S20，對氧化鎂鋅合成篩選粉末進行胚化處理，以得到氧化鎂鋅合成生胚。最後，將氧化鎂鋅合成生胚放入第一高溫爐中，並通入如氮氣或氬氣之惰性氣體，且以攝氏1300～1500度、5～80千帕(kPa)、3-18小時進行高溫燒結，以得到摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材。在燒結過程中，使ⅢA族元素能夠進行取代反應，如鋁、鎵、銦取代氧化鎂鋅中鋅的晶格位置，每個取代反應會多釋放出一個自由電子，以降低其電阻係數。再者，藉由惰性氣體的通入，可幫助氧化鎂鋅中，氧空缺的生成，每個氧空缺會多釋放出兩個自由電子，亦可降低其電阻係數。In the next step, as shown in step S16, the magnesium zinc oxide synthetic powder is added to the polyvinyl alcohol (PVA) as an adhesive, and the mixture is ground and granulated to increase the fluidity of the powder, thereby obtaining a magnesium sulphate synthetic granulated powder. . After the granulated powder is obtained, as shown in step S18, the magnesia-zinc synthetic granulated powder is sieved by a sieve to obtain a magnesia-zinc synthetic screening powder, wherein the size of the sieve is 100 to 600 mesh (mesh) ). Then, in step S20, the magnesium oxide zinc synthetic screening powder is subjected to an embryonic treatment to obtain a magnesium oxide zinc synthetic raw embryo. Finally, the magnesium oxide zinc synthetic raw embryos are placed in a first high temperature furnace and passed through an inert gas such as nitrogen or argon, and at 1300 to 1500 degrees Celsius, 5 to 80 kilopascals (kPa), 3 to 18 hours. High temperature sintering is performed to obtain a magnesium oxide zinc sputtering target doped with a Group IIIA element. During the sintering process, the Group IIIA element can be subjected to a substitution reaction, such as aluminum, gallium, indium, and the lattice position of zinc in the zinc oxide, and each substitution reaction releases a free electron to reduce its resistivity. Furthermore, the introduction of an inert gas can help the formation of oxygen vacancies in the magnesium oxide zinc, and each oxygen vacancy will release two free electrons, and the resistivity can also be lowered.
在上述步驟S20係更包含下列步驟，如第5圖所示。在完成步驟S18後，係進行步驟S202，即將氧化鎂鋅合成篩選粉末置入模具中，以油壓機製成氧化鎂鋅合成初胚，其中油壓機之壓力設定為20～600公斤/平方公分。接著，如步驟S204所示，將氧化鎂鋅合成初胚進行冷均壓(CIP，cold isostatic pressure)處理，以消除模具在製造過程中產生之應力，其中冷均壓處理之壓力為100～300百萬帕(MPa)。最後如步驟S206所示，將氧化鎂鋅合成初胚置入第二高溫爐中，以攝氏600-800度進行高溫加熱，以去除黏著劑，並獲得上述之氧化鎂鋅合成生胚，以供燒結之用。In the above step S20, the following steps are further included, as shown in FIG. 5. After the step S18 is completed, the step S202 is performed, in which the magnesium oxide zinc synthetic screening powder is placed in a mold, and the magnesia-zinc synthetic initial embryo is prepared by an oil press, wherein the pressure of the hydraulic press is set to 20 to 600 kg/cm 2 . Next, as shown in step S204, the magnesium oxide zinc is synthesized into a cold isostatic pressure (CIP) treatment to eliminate the stress generated in the manufacturing process of the mold, wherein the pressure of the cold equalization treatment is 100-300. Million Pascals (MPa). Finally, as shown in step S206, the magnesia-zinc-synthesized primary embryo is placed in a second high-temperature furnace, and heated at a high temperature of 600-800 degrees Celsius to remove the adhesive, and the above-mentioned magnesium-zinc-synthesized raw embryo is obtained for For sintering.
前在工業上製備透明導電氧化(TCO)薄膜的主要製程為磁控濺鍍法。工業上常使用磁控濺鍍法鍍製TCO薄膜的優勢在於1.可高速鍍膜、2.可大面積鍍膜、3.可降低操作壓力、4.可對不規則形狀基材均勻鍍膜及5.可降低鍍膜溫度。因應磁控濺鍍法之優勢，本發明所製備出的的濺鍍靶材，不但具有高緻密度與低電阻係數，且亦可作為磁控濺鍍法之濺鍍靶材，此種靶材能克服因靶材表面微粒(nodules)的生成，所衍生之濺鍍過程中異常電弧放電(arcing)導致之薄膜性質劣化，與因靶材表面微粒去除所造成之停工損失、生產效率下降及生產成本提高等問題。The main process for preparing transparent conductive oxidation (TCO) films in the industry before is the magnetron sputtering method. The advantages of electroplating TCO film plating in the industry are as follows: 1. High-speed coating, 2. Large-area coating, 3. Lower operating pressure, 4. Uniform coating on irregularly shaped substrates and 5. Can reduce the coating temperature. In view of the advantages of the magnetron sputtering method, the sputtering target prepared by the invention not only has high density and low resistivity, but also can be used as a sputtering target for magnetron sputtering, such a target. It can overcome the degradation of film properties caused by abnormal arcing during the sputtering process caused by the formation of nodules on the target surface, and the loss of work due to particle removal on the surface of the target, production efficiency degradation and production. Problems such as increased costs.
再者，對於銅銦鎵硒(CuInGaSe2,CIGS)太陽能電池而言，為了配合作為緩衝層之氧化鎂鋅(MZO)層之晶格，利用本發明製備之摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材，於緩衝層上形成上電極與窗層結構，不但能增加紅外光穿透，亦能提高導電特性，同時也因為結構接近，所以可減少與氧化鎂鋅層發生晶格不匹配之問題。Furthermore, for a CuInGaSe 2 (CIGS) solar cell, in order to match the crystal lattice of the magnesium zinc oxide (MZO) layer as a buffer layer, the magnesium oxide doped with a Group IIIA element prepared by the present invention is used. The sputtering target forms the upper electrode and the window layer structure on the buffer layer, which not only increases the penetration of infrared light, but also improves the electrical conductivity, and also reduces the lattice mismatch with the magnesium oxide zinc layer because of the close structure. The problem.
以MZO為例，氧化鎂(MgO)能隙約7.7電子伏特(ev)，摻雜於氧化鋅(ZnO)中，當MgO的摻雜量為0.35時(x=0.35)，不僅可使ZnO的能隙值由原有的3.2 eV提升至超過4.0 eV，且其結構仍保持ZnO之六方纖鋅礦結構。因此，本發明所製備出的摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材，於CIGS太陽能元件上形成TCO上電極與窗層材料，係為氧化鋁鎂鋅(Al:MgxZn1-xO,AMZO)、氧化鎵鎂鋅(Ga:MgxZn1-xO,GMZO)或氧化銦鎂鋅(In:MgxZn1-xO,IMZO)等XMZO(X=Al,Ga,or In)之材料。在XMZO中可藉由摻雜ⅢA族的氧化物，來提高MZO的導電特性，以達到作為TCO上電極材料之導電特性要求。而原本MZO中氧化鎂之寬能隙的特性，能增加XMZO的光學能隙，來增加近紅外光之穿透，如現有的氧化鋁鋅(AZO)能隙約在3.4eV，AMZO的能隙約在3.4~3.8eV甚至更高，能夠可調整性的選擇光吸收的波段。最後利用摻雜比例的控制，來調整薄膜的能隙值，使吸收邊界(absorption edge)產生藍移現象(blue shift)，進而改善TCO層之整體透光效率。Taking MZO as an example, the magnesium oxide (MgO) energy gap is about 7.7 electron volts (ev), which is doped in zinc oxide (ZnO). When the doping amount of MgO is 0.35 (x=0.35), not only ZnO can be used. The energy gap is increased from the original 3.2 eV to over 4.0 eV, and its structure still maintains the hexagonal wurtzite structure of ZnO. Therefore, the magnesium oxide zinc sputtering target doped with a group IIIA element prepared by the invention forms a TCO upper electrode and a window layer material on the CIGS solar element, and is a magnesium magnesium zinc oxide (Al: Mg x Zn 1- x O, AMZO), gallium zinc oxide (Ga: Mg x Zn 1-x O, GMZO) or indium magnesium zinc oxide (In: Mg x Zn 1-x O, IMZO), etc. XMZO (X = Al, Ga, Or In) material. In XMZO, the conductivity of MZO can be improved by doping the oxide of Group IIIA to achieve the conductivity characteristics of the electrode material as TCO. The wide energy gap of magnesium oxide in MZO can increase the optical energy gap of XMZO to increase the penetration of near-infrared light. For example, the existing aluminum-zinc (AZO) energy gap is about 3.4 eV, the gap of AMZO. About 3.4~3.8eV or higher, it is possible to adjust the band of light absorption. Finally, the control of the doping ratio is used to adjust the energy gap value of the film, so that the absorption edge produces a blue shift, thereby improving the overall light transmission efficiency of the TCO layer.
以下介紹實際製備摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材的過程。首先將Mg0.06Zn0.94O之氧化鎂鋅之粉末摻雜重量百分比為2%之氧化鋁，放入球磨罐中加入乙醇及鋯球球磨16小時，然後將球磨後之漿料之入烘箱中，以攝氏80度乾燥至粉末恆重為止，將乾燥之粉末放入高溫爐中，在650℃反應3小時，以得到AMZO合成粉末。然後在AMZO合成粉末中加入重量百分比為2%之PVA後，再次置入烘箱中，以攝氏80度乾燥至恆重為止，將恆重之AMZO粉末研磨且經由100 mesh的篩網過篩，在將過篩之粉末，製入模具中以油壓壓製成初坯，壓力為80公斤/平方公分，再將初坯以CIP強化，且放入高溫爐中經由攝氏600℃脫蠟，獲得AMZO生胚，最後將AMZO在高溫爐中通入氬氣作為燒結之氣氛，並將壓力維持在50千Pa以攝氏1400度持溫3小時，即可獲得高緻密度及低電阻係數之AMZO濺鍍靶材。The process of actually preparing a magnesium oxide zinc sputtering target doped with a Group IIIA element is described below. First, Mg 0.06 Zn 0.94 O powder of magnesium oxide zinc is doped with alumina of 2% by weight, placed in a ball mill tank, and then ball milled with ethanol and zirconium balls for 16 hours, and then the ball milled slurry is placed in an oven. After drying to 80 ° C to a constant weight of the powder, the dried powder was placed in a high temperature furnace and reacted at 650 ° C for 3 hours to obtain an AMZO synthetic powder. Then, PVA was added to the AMZO synthetic powder in a weight percentage of 2%, and then placed in an oven again, and dried to a constant weight at 80 ° C. The constant weight AMZO powder was ground and sieved through a 100 mesh sieve. The sieved powder is put into a mold and pressed into a preform by oil pressure at a pressure of 80 kg/cm 2 , and then the preform is reinforced with CIP and placed in a high temperature furnace to be dewaxed at 600 ° C to obtain AMZO. Embryo, finally AMZO is argon gas in a high temperature furnace as a sintering atmosphere, and the pressure is maintained at 50 kPaPa at 1400 ° C for 3 hours to obtain a high density and low resistivity AMZO sputtering target. material.
另外將所獲得之AMZO之靶材以X射線繞射(XRD)進行分析，如第6圖所示，此繞射圖譜，與國際標準圖譜氧化鋅之結構完全相符合，證實所獲得的結構為氧化鋅之纖鋅礦結構。In addition, the obtained target of AMZO is analyzed by X-ray diffraction (XRD). As shown in Fig. 6, the diffraction pattern is completely consistent with the structure of the international standard map zinc oxide, and the obtained structure is confirmed to be Zinc ore structure of zinc oxide.
再將所獲得之AMZO靶材進行物性之分析，此結果證實了，本發明可製備緻密度高達98.54%及電阻率低至2.8x10-3歐姆-公分(Ω-cm)之AMZO靶材。The obtained AMZO target was analyzed for physical properties. This result confirmed that the present invention can produce an AMZO target having a density of up to 98.54% and a resistivity as low as 2.8 x 10 -3 ohm-cm (Ω-cm).
最後將AMZO靶材利用射頻(RF)磁控濺鍍在康寧玻璃基板上進行AMZO薄膜鍍製，以1.5x10-5托爾(torr)、工作壓力為3x10-3 torr、濺鍍功率為80瓦(W)，薄膜沉積時間為10分鐘，氬氣流量為10立方公分/分鐘(sccm)，及基板溫度為攝氏270度。由第7圖可證實能夠獲得AMZO薄膜，且藉由四點探針量測之電阻係數為1.2x10-3 Ω-cm，證實所製備之高緻密度且低電阻係數之XMZO靶材能夠用於濺鍍製程。Finally, the AMZO target was sputtered on a Corning glass substrate by radio frequency (RF) magnetron sputtering for AMZO thin film, with a 1.5x10 -5 torr, a working pressure of 3x10 -3 torr, and a sputtering power of 80 watts. (W), the film deposition time was 10 minutes, the argon gas flow rate was 10 cubic centimeters per minute (sccm), and the substrate temperature was 270 degrees Celsius. It can be confirmed from Fig. 7 that the AMZO film can be obtained, and the resistivity of the four-point probe is 1.2 x 10 -3 Ω-cm, and it is confirmed that the prepared high-density and low-resistance XMZO target can be used. Sputtering process.
另外，如第8圖所示，當濺鍍功率由40 W提升至100 W時，可證實AMZO薄膜在300-1200奈米(nm)的平均穿透度皆達87%以上，並且經由穿透圖譜換算可得其AMZO薄膜的能係值由AZO之原3.3 eV提升到約3.7 eV，表示MgO有成功摻雜於ZnO晶格中。In addition, as shown in Figure 8, when the sputtering power is increased from 40 W to 100 W, it can be confirmed that the AMZO film has an average penetration of more than 87% at 300-1200 nm (nm) and passes through The conversion of the spectrum of the AMZO film can be increased from AZO's original 3.3 eV to about 3.7 eV, indicating that MgO is successfully doped in the ZnO lattice.
綜上所述，本發明製備的靶材，不但可作為磁控濺鍍使用的靶材，且此靶材於CIGS太陽能電池上所形成之上電極與窗層材料，亦可提高整體太陽光穿透率。In summary, the target prepared by the invention can be used not only as a target for magnetron sputtering, but also the upper electrode and the window layer material formed on the CIGS solar cell can improve the overall sunlight penetration. Transmittance.
以上所述者，僅為本發明一較佳實施例而已，並非用來限定本發明實施之範圍，故舉凡依本發明申請專利範圍所述之形狀、構造、特徵及精神所為之均等變化與修飾，均應包括於本發明之申請專利範圍內。The above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, so that the shapes, structures, features, and spirits described in the claims of the present invention are equally varied and modified. All should be included in the scope of the patent application of the present invention.
10．．．氧化鋁鋅薄膜10. . . Alumina zinc film
12．．．本質氧化鋅層12. . . Essential zinc oxide layer
14．．．硫化鎘層14. . . Cadmium sulfide layer
第1圖為先前技術之銅銦鎵硒太陽能電池結構剖視圖。1 is a cross-sectional view showing the structure of a prior art copper indium gallium selenide solar cell.
第2圖為先前技術之銅銦鎵硒太陽能電池之光波長與反射率曲線圖。Figure 2 is a graph of light wavelength and reflectance of a prior art copper indium gallium selenide solar cell.
第3圖為先前技術之銅銦鎵硒太陽能電池之基板溫度與電阻率曲線圖。Figure 3 is a graph showing the substrate temperature and resistivity of a prior art copper indium gallium selenide solar cell.
第4圖為本發明之製備濺鍍靶材之流程圖。Figure 4 is a flow chart of the preparation of a sputtering target of the present invention.
第5圖為本發明之胚化處理之流程圖。Figure 5 is a flow chart of the embryonic treatment of the present invention.
第6圖為本發明之摻雜ⅢA族元素之氧化鎂鋅濺鍍靶材之X射線繞射(XRD)分析圖。Fig. 6 is an X-ray diffraction (XRD) analysis chart of a magnesium oxide zinc sputtering target doped with a Group IIIA element of the present invention.
第7圖為本發明之利用射頻磁控濺鍍鍍製之摻雜ⅢA族元素之氧化鎂鋅薄膜之X射線繞射分析圖。Fig. 7 is an X-ray diffraction analysis diagram of a magnesium oxide-zinc film doped with a Group IIIA element by radio frequency magnetron sputtering according to the present invention.
第8圖為本發明之利用射頻磁控濺鍍鍍製之摻雜ⅢA族元素之氧化鎂鋅薄膜之光學穿透圖譜。Figure 8 is an optical transmission diagram of a magnesium oxide-zinc film doped with a Group IIIA element by radio frequency magnetron sputtering according to the present invention.
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| US10651218B1 (en) | 2019-01-03 | 2020-05-12 | Vanguard International Semiconductor Corporation | Optical sensor structure and method for forming the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220037561A1 (en) * | 2018-09-26 | 2022-02-03 | Idemitsu Kosan Co.,Ltd. | Oxide stacked body and method for producing the same |
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| TW201337014A (en) | 2013-09-16 |
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