201022461 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種太陽能選擇性吸收膜及其製造方 法，特別有關於一種具高選擇比的單層太陽能選擇性吸收 膜及其製造方法。 【先前技術】 雙陶瓷合金層結構應用於太陽能選擇性吸收膜的研究 φ 開發始於1990年代。雙陶瓷合金層結構’例如金屬-氮化 鋁(M-A1N)和金屬-氧化鋁(M-Al2〇3)，傳統上是使用一種雙 靶材直流電磁控管電漿濺鍍技術（two-target DC magnetron plasma sputtering technology)來製備，應用於太陽能選擇 性吸收膜，可得到非常高的光熱轉換效率。 傳統之選擇性吸收膜製程大部份是利用雙靶材濺鍍產 生的複合膜’例如以不鏽鋼與鋁的雙靶材製程，製作陶竞 金屬膜(Cermet)做為選擇性吸收膜。適當的金屬陶瓷複合膜 •厚度與金屬分率，可在太陽能輻射區域表現出高吸收而對 熱輻射（紅外線區域)表現出高度反射性。該複合物沈積在 對紅外線反射的金屬基材上可以形成太陽能選擇性吸收 膜。 第1圖係顯示傳統多層選擇性吸收膜結構製作於金屬 基材的剖面示意圖。於第！圖中，傳統多層選擇性吸收膜 結構m-130以雙或多乾材滅鍍方式形成於金屬基材刚 ^及收臈結構mm具漸進式的的光學特性，亦即各 曰、斤射率⑻、消光係數(k)、膜厚(d)均不同。欲達到對太 3 201022461 陽能輻射區域具高吸收性而對熱辕射(紅外線區域)具高度 反射性的選擇性，習知技術需仰賴多層陶究金屬膜(c_et) 結構，方能達到所欲的特性。再者，多層陶竟金屬膜(cermet) 需依賴多靶多腔體製程，耗費製造資源及成本。 近年來，業界已開始研九開發單革巴材賤鍵選擇性吸收 膜。雖然單無材製程優於雙㈣製程， 間及成本，但在單钟製程下，單時分擔傳統;201022461 VI. Description of the Invention: [Technical Field] The present invention relates to a solar selective absorbing film and a method of manufacturing the same, and more particularly to a single-layer solar selective absorbing film having a high selectivity and a method of manufacturing the same. [Prior Art] The application of a double ceramic alloy layer structure to a solar selective absorbing film φ Development began in the 1990s. Double ceramic alloy layer structures such as metal-aluminum nitride (M-A1N) and metal-alumina (M-Al2〇3), traditionally using a dual target DC electromagnetic tube plasma sputtering technique (two- Target DC magnetron plasma sputtering technology), which is applied to solar selective absorption film, can obtain very high photothermal conversion efficiency. Conventional selective absorption film processes are mostly made up of composite films produced by double target sputtering. For example, a stainless steel and aluminum double target process is used to make Cermet as a selective absorption film. Appropriate cermet composite film • Thickness and metal fraction, which exhibits high absorption in the solar radiation area and highly reflective heat radiation (infrared area). The composite is deposited on a metal substrate that is reflective to infrared light to form a solar selective absorbing film. Fig. 1 is a schematic cross-sectional view showing the structure of a conventional multilayer selective absorbing film formed on a metal substrate. In the first! In the figure, the conventional multilayer selective absorption film structure m-130 is formed by double or multiple dry material de-plating in the metal substrate and the shrinkage structure mm has a progressive optical property, that is, each 曰, 斤 率 rate (8) The extinction coefficient (k) and film thickness (d) are all different. In order to achieve high reflectivity for the solar radiation zone of Tai 3 201022461 and highly reflective selectivity for thermal radiation (infrared region), the conventional technology relies on the multi-layer ceramic film (c_et) structure to achieve Desirable characteristics. Furthermore, the multi-layer ceramic film (cermet) relies on a multi-target multi-cavity process, which consumes manufacturing resources and costs. In recent years, the industry has begun to develop a selective adsorption film for the single-grain material. Although the single materialless process is superior to the double (four) process, between the cost and the cost, in the single clock process, the single time sharing tradition;
Ο 把的金屬層㈣，錢氛及功率的控制上較 雙把製料求要更料’仙㈣加料朗較控制困 難性。 【發明内容】 本發明之實施例提供一種太陪At 古木,^ ^ 璉擇性吸收膜的製造 方法’包括：提供〆基材於一直处 .Μ . ，触 -二賤鑛腔體中；以及濺鍍 一金屬同時通入一氣體，以形成—^ ^ 早層金屬-陶瓷複合膜於 該基材上，其中該乎層金屬-陶蔡益 t後合膜具有吸收可見光 反射紅外光的性質。 π叹队』兄尤且 本發明之實施例另提供一稽+ ^ 太陽能選擇性吸收膜，包 括.一基材；以及〆早層金屬、陶垄… 層金屬-陶《複合膜具有吸收可見光外= 為使本發明能更明顯易t董，γ + 所附圖式，作詳細説明如下： 、牛實施例’並配合 【實施方式】 .201022461 以下以各實施例詳細說明並伴隨著圖式說明之範例， 做為本發明之參考依據。在圖式或說明書描述中，相似或 相同之部分皆使用相同之圖號。且在圖式中，實施例之形 狀或是厚度可擴大，並以簡化或是方便標示。再者，圖式 中各元件之部分將以分別描述說明之，值得注意的是，圖 中未繪示或描述之元件，為所屬技術領域中具有通常知識 者所知的形式，另外，特定之實施例僅為揭示本發明使用 之特定方式，其並非用以限定本發明。 ❿ 本發明之實施例提出一種製備單層陶瓷-金屬結構及 方法，作為太陽能選擇性吸收膜，經過光學模擬預先計算 該單層吸收膜最適當的光學常數，包括折射率(η)、消光係 數(k)、膜厚（d)，亦即模擬計算出單層陶金吸收膜所需的金 屬含量與鍍膜厚度。 第2A-2C圖係顯示根據本發明之一實施例的太陽能選 擇性吸收膜製造方法的剖面示意圖。請參閱第2A圖，首 先提供一基材200於一真空單靶材濺鍍腔體中，濺鍍一金 ⑩屬同時通入一氣體，以形成一單層金屬-陶瓷複合膜210於 該基材200上。該單層金屬-陶瓷複合膜具有吸收可見光且 反射紅外光的性質。 請參閱第2B圖，在經過自然大氣下曝曬L，利用高金 屬分率的吸收膜表面之金屬原子與大氣中的氧原子形成氧 化物薄層215。應注意的是，該氧化物薄層215亦為一光 學薄膜，經匹配設計可有效減少太陽光的反射率，達抗反 射效果，亦提升選擇性吸收膜的吸收效能。並該氧化物之 材料特性具有抗腐蝕特性，亦即防止氧原子的氧化擴散， 5 201022461 可達到吸收膜與大氣的阻隔效果，對產品在日光下曝曬有 性能穩定、抗老化之特性。 本發明另一實施例樣態為提供一種單一金屬靶材，利 用真空濺鍍法製作太陽能選擇性吸收膜。在真空濺鍍製程 中，以鋁金屬靶材為例子，調整特定氣氛及功率即可使電 漿轟擊/銘金屬原子’被擊出之㈣子在與通人之反應氣 體（氮氣）產生反應，並沉積於基板上形成金屬_陶瓷複合 ❿ 膜’即陶金膜(eennet film)。此陶金膜對太陽光有很好的吸 收效果。根據本發明之一實施例，利用高金屬分率的陶金 J來進行自然表面氧化，來自然形成一層氧化物薄膜。該 薄膜可作為抗反射層，同時增加入射光的通量，提 升吸收臈的吸收率。 作方:、Γ主：：疋’本發明實施例的太陽能選擇性吸收膜製 形成抗反射效果，無須層吸收膜’並;然曝· 製程的操作成本與提料;：二熱處理，可降低真空舰 相較於習知技術，鍍製程的量產能力。 更明確地說，以單金屬ί月之實施例將雙_為單把。 金屬做為进_材，在;;例如銘(αι)乾、鈦⑽乾或其他 太陽能選擇性吸收膜。氣氛下，利用真空賊製作 性雜法製備太陽能選==另-糊’利用反應 再者，本發明眘膜° 應濺鍍參數，域料碰計算，控制特定反 製備出特定光學常數a ^反應氣氛濃度、濺鍍時間， 腸層’使太陽能選擇性吸收膜僅需 6 .201022461 錢鑛單一層吸收膜，即可所欲的光學效能。該吸收膜層為 陶究-金屬之薄膜結構，在可見光與近紅外光波段有高吸 收’在遠紅外波段有高反射。經過自然曝曬，利用大氣中 的氧原子來進行吸收膜表面的氧化，表面形成一層氧化物 薄膜。該氧化物薄層亦為一光學薄臈，可有效減少太陽光 的反射率，及提升選擇性吸收膜的吸收效能。並該氧化物 之材料特性具有抗腐蝕特性，亦即防止氧原子的氧化擴 散，可達到吸收膜與大氣的阻隔效果，對產品在日光下曝 ❿曬有性能穩定、抗老化之特性。 光學模擬 第3圖係顯示本發明實施例的光學模擬步驟，並對應 以第2A_2C圖實施的流程示意圖。首先利用在不同氮化程 度下的單層膜（陶金層吸收膜）之光學常數來模擬最適之光 學特性’即有較低的反射率（步驟330)。接著，附加一層氧 化層來模擬吸收膜經大氣曝曬氧化時所產生之氧化屏，即 進行雙層膜匹配(步驟320)。最後，模擬計算單層吸I膜與 附加氧化層之選擇性吸收膜效能（吸收率），如步驟33〇所 示0 有鑑於此，本發明各實施例僅需濺鍍單層吸收臈，故 光學模擬中呈現不同氮化程度與不同膜厚度之單層膜。表 1係顯示模擬背景是以鋁靶(A1)為靶材基礎，在不同N濃 度氣氛(3-12%)下進行反應性濺鍍。由此可形成不同氮化程 度之一系列的陶瓷-金屬單層膜，並分析其光學特性，包= 反射率（Reflectance，％)。除了模擬不同金屬分率的單声 膜，同時也模擬不同膜厚下（30-120nm)的結果。因為 7 201022461 同的膜厚會產;^ 不同的光學干涉效果，而產生特定的光學 特性影響，如5身 射率與截止波長位置等。在表1的模擬結 果中，當氮氣5詹# 上-於不同金屬分率及膜厚下之反射率 媒且姐絲 ---Ο The metal layer (4), the control of the money and the power are more demanding than the double-handling materials, and the sacred (four) feeding is more difficult to control. SUMMARY OF THE INVENTION Embodiments of the present invention provide a method for fabricating a absorbing coating film that includes a ruthenium substrate, including: providing a ruthenium substrate in a ruthenium, a touch-diode ore cavity; A metal is sputtered while a gas is introduced to form an early-layer metal-ceramic composite film on the substrate, wherein the layer metal-Taocai t-after film has the property of absorbing visible light to reflect infrared light. The π squad brother and the embodiment of the present invention further provide a solar selective absorbing film comprising: a substrate; and an early layer of metal, terracotta ... layer metal - ceramic "composite film has absorption of visible light In order to make the present invention more conspicuous, the γ + drawing will be described in detail as follows: , cattle embodiment 'and cooperate with the embodiment 】 201022461 The following is a detailed description of each embodiment and accompanied by a schematic description The examples are based on the present invention. In the drawings or the description of the specification, the same drawing numbers are used for similar or identical parts. In the drawings, the shape or thickness of the embodiment may be expanded and simplified or conveniently indicated. In addition, the components of the drawings will be described separately, and it is noted that the components not shown or described in the drawings are known to those of ordinary skill in the art, and in particular, The examples are merely illustrative of specific ways of using the invention and are not intended to limit the invention.实施 Embodiments of the present invention provide a single-layer ceramic-metal structure and method for pre-calculating the most suitable optical constants of the single-layered absorption film, including refractive index (η), extinction coefficient, as a solar selective absorption film. (k), film thickness (d), that is, the metal content and coating thickness required for the calculation of the single-layer ceramic gold absorbing film. 2A-2C is a schematic cross-sectional view showing a method of fabricating a solar selective absorbing film according to an embodiment of the present invention. Referring to FIG. 2A, a substrate 200 is first provided in a vacuum single target sputtering chamber, and a gold 10 is sputtered while a gas is introduced to form a single metal-ceramic composite film 210. On the material 200. The single-layer metal-ceramic composite film has a property of absorbing visible light and reflecting infrared light. Referring to Fig. 2B, after exposure to L in a natural atmosphere, a thin layer 215 of oxide is formed by metal atoms on the surface of the absorbing film having a high metal fraction and oxygen atoms in the atmosphere. It should be noted that the oxide thin layer 215 is also an optical film, and the matched design can effectively reduce the reflectance of sunlight, achieve anti-reflection effect, and improve the absorption efficiency of the selective absorption film. And the material properties of the oxide have anti-corrosion properties, that is, prevent oxidation diffusion of oxygen atoms, 5 201022461 can achieve the barrier effect of the absorption film and the atmosphere, and have stable performance and anti-aging properties for the product to be exposed to sunlight. Another embodiment of the present invention provides a single metal target for producing a solar selective absorbing film by vacuum sputtering. In the vacuum sputtering process, taking an aluminum metal target as an example, adjusting the specific atmosphere and power can cause the plasma bombardment/metal atom to be shot out (four) to react with the reaction gas (nitrogen). And deposited on the substrate to form a metal-ceramic composite ruthenium film, that is, an eennet film. This pottery film has a good absorption effect on sunlight. According to an embodiment of the present invention, the natural surface oxidation is performed using a high metal fraction of the pottery J to naturally form an oxide film. The film acts as an anti-reflective layer while increasing the flux of incident light and increasing the absorption of the absorbing enthalpy. The method: Γ :: 疋 'The solar selective absorbing film of the embodiment of the invention forms an anti-reflection effect, without the need for a layer of absorbing film 'and; the exposure and process operation costs and materials; 2 heat treatment, can be reduced Compared with the prior art, the vacuum ship has the mass production capability of the plating process. More specifically, in the embodiment of the single metal ί月, the double _ is a single handle. Metal is used as a material, such as; (Im) dry, titanium (10) dry or other solar selective absorbing film. Under the atmosphere, the vacuum thief is used to make solar energy selection == another-paste' use reaction, the invention is careful to reflect the sputtering parameters, the domain material is calculated, and the specific optical constant is prepared to control the specific optical constant a ^ reaction Atmospheric concentration, sputtering time, and intestinal layer make the solar selective absorption film only need 6.201022461 money ore single layer absorption film, which can achieve the desired optical performance. The absorbing film layer is a ceramic-metal film structure with high absorption in the visible and near-infrared light bands and high reflection in the far infrared band. After natural exposure, oxygen atoms in the atmosphere are used to oxidize the surface of the absorption film, and an oxide film is formed on the surface. The oxide thin layer is also an optical thin crucible, which can effectively reduce the reflectance of sunlight and enhance the absorption efficiency of the selective absorption film. The material properties of the oxide have anti-corrosion properties, that is, prevention of oxidation and diffusion of oxygen atoms, and the barrier effect of the absorption film and the atmosphere can be achieved, and the product has stable performance and anti-aging properties when exposed to sunlight. Optical Simulation Fig. 3 is a flow chart showing the optical simulation steps of the embodiment of the present invention and corresponding to the second embodiment. First, the optical constants of a single layer film (the gold layer absorbing film) under different nitriding degrees are used to simulate the optimum optical characteristics, i.e., have a lower reflectance (step 330). Next, an additional oxide layer is applied to simulate the oxidation screen produced by the absorption film during atmospheric exposure oxidation, i.e., double layer film matching (step 320). Finally, the selectivity of the selective absorption film (absorption rate) of the single-layer I and the additional oxide layer is simulated, as shown in step 33. In view of this, the embodiments of the present invention only need to be sputtered with a single layer of absorption enthalpy. Single layer films of varying degrees of nitridation and different film thicknesses are presented in optical simulations. Table 1 shows that the simulated background is based on the aluminum target (A1) and reactive sputtering is performed under different N concentration atmospheres (3-12%). Thus, a ceramic-metal monolayer film of one series of different nitridation degrees can be formed, and its optical characteristics can be analyzed, including reflectance (Reflectance, %). In addition to simulating monophonic films with different metal fractions, the results at different film thicknesses (30-120 nm) were also simulated. Because 7 201022461 the same film thickness will be produced; ^ different optical interference effects, resulting in specific optical characteristics, such as 5 body rate and cutoff wavelength position. In the simulation results in Table 1, when the nitrogen 5 zh # on - different metal fractions and film thickness reflectance medium and sister silk ---
步驟一： 屣度為7·5%且膜厚達90nm時，有較低的反 射率表1 即在單層的吸收膜特性中，有較高的吸收率。 改變大範圍（30-120nm)之膜厚以尋找較佳之膜厚，並找 出較合適薄膜之金屬分率。模擬具最佳性能的 Α1/Α1Ν-Α12〇3做為選擇性吸收臈，其吸收率如表！所示， Φ 其中氧化層是以氧化紹作為氧化層。 步驟二： 比較不同膜厚下之反射率’並找出較合適的薄膜厚 度。根據表1的模擬結果顯示，薄膜於氮氣氛率7 5%及薄 膜厚度90nm時具有最低之反射率，故於膜厚9〇nm附近小 I請尋找最佳之薄膜厚度’如表2所示，根據模擬結果顯 示為95nm。 8 201022461 表2、比較不同膜厚下之反射率 d(nm) R°/〇 80 19.46 90 18.62 95 18.58 100 18.76 步驟三： 比較不同金屬分率之薄膜於膜厚95nm下之單層及雙 層之吸收率。因為第二層膜厚之限制，且其作用為“抗反 ❹射”效果，故第二層膜對吸收率僅些微貢獻。若能突破氧 化層的膜厚限制，則有利於達到更佳的抗反射效果。表3 列出單、雙層膜吸收率之比較差異。單層鋁陶金膜其厚度 為95nm，第二層氧化铭膜其厚度20nm。該結果顯示，實 施例的模擬組別中，C組有較佳的結果顯示，吸收率可達 Q.8。 表3、比較單雙層膜之吸收率 樣品編"5^» A B C D E F N2% (1st layer) 3% 6% 7.5% 9% 10.5% 12% 單層膜吸收率 0.50 0.66 0.75 0.75 0.49 0.22 雙層膜吸收率 0.59 0.72 0.80 0.77 0.45 0.20 第4與5圖分別顯示根據本發明實施例在不同氮化程 度下的單、雙層膜的反射光譜示意圖，其中單層膜為不同 金屬分率之鋁陶金單層膜，雙層膜分別為第一層的鋁陶金 膜及第二層的氧化鋁膜。請參閱第4與5圖，分別比對樣 品編號40a-40f和50a-50f，可發現C組別（40c和50c)之反 9 201022461 射率較低且截止波長發生在較長波長之位置1400nm，故其 吸收率也較佳。在後續的研究中可以利用不同氮化氣氛濃 度與不同膜厚來進行匹配，找出截止波長發生在1600nm 位置的單層吸收膜。 比較第4與5圖中效果最好的C組別，將其重新繪製 如第6圖所示。其中，於單、雙層膜反射率中，第二層膜 有往長波長方向移動，且整體反射率都有下降的趨勢，故 雙層膜之吸收率0.8較單層膜吸收率0.75來的高。因此， ❹在本發明實施例中，以選擇適合的單層吸收膜即可達到高 的吸收率0.75 ’並該單層吸收膜具有選擇性特性，在可見 光與近紅外光區有高吸收，並在遠紅外光區有反射特性。 §經放置於大氣中自然加熱氧化，自然形成一薄層氧化 膜’則可達抗反射效果，並提升選擇性吸收膜之吸收效能。 目前的實施例模擬中，除了具選擇性的特性以外，吸收率 可達0.8。 濺鍍製備 濺鍍實驗製備一系列不同氮化程度之陶金薄膜，並同 時了解單層選擇性吸收膜之性能，及實際進行曝曬，分析 其氧化（老化）之情形。首先鍍製金屬鋁膜12片，做為A1 基板，在每一不同氣氛濺鍍條件下，放入2片A1基板和1 片玻璃基板。濺鍍完成後，將A1基板上之薄膜進行反射 率、放射率、吸收率之量測。將鍍於玻璃基板之薄膜以橢 圓儀分析光學常數及膜厚。表4為鍍膜實驗之參數’濺鍍 壓力約為2mtorr，Ar流量固定為40sccm，氮氣流量為 〇-4sccm ’濺鍍功率為150W，鍍製10分鐘。 10 201022461Step 1: When the twist is 7.5% and the film thickness is 90 nm, there is a lower reflectance. Table 1 shows that the absorption coefficient of the single layer has a higher absorption rate. Change the film thickness over a wide range (30-120 nm) to find a better film thickness and find the metal fraction of the appropriate film. Simulating the best performance of Α1/Α1Ν-Α12〇3 as a selective absorption 臈, its absorption rate is as shown! As shown, Φ wherein the oxide layer is an oxide layer. Step 2: Compare the reflectance at different film thicknesses' and find a suitable film thickness. According to the simulation results in Table 1, the film has the lowest reflectance at a nitrogen atmosphere rate of 75% and a film thickness of 90 nm. Therefore, look for the best film thickness at a film thickness of about 9 〇 nm as shown in Table 2. According to the simulation results, it is displayed as 95 nm. 8 201022461 Table 2. Comparison of reflectance d(nm) at different film thicknesses R°/〇80 19.46 90 18.62 95 18.58 100 18.76 Step 3: Comparing single and double layers of films with different metal fractions at a film thickness of 95 nm Absorption rate. Because of the limitation of the film thickness of the second layer, and its effect is "anti-reflective" effect, the second film only contributes slightly to the absorption rate. If it can break through the film thickness limit of the oxide layer, it will help to achieve better anti-reflection effect. Table 3 shows the difference in the absorption rates of single and double membranes. The single-layer aluminum ceramic gold film has a thickness of 95 nm, and the second layer is oxidized to a thickness of 20 nm. The results show that among the simulation groups of the examples, the C group has better results, and the absorption rate can reach Q.8. Table 3. Comparison of Absorption Rate of Single Bilayer Films "5^» ABCDEF N2% (1st layer) 3% 6% 7.5% 9% 10.5% 12% Monolayer Membrane Absorption Rate 0.50 0.66 0.75 0.75 0.49 0.22 Double Layer Membrane Absorption Rate 0.59 0.72 0.80 0.77 0.45 0.20 Figures 4 and 5 respectively show the reflection spectra of single and double-layer films at different nitridation degrees according to an embodiment of the present invention, wherein the monolayer film is an aluminum ceramic of different metal fractions. The gold single layer film is a first layer of aluminum pottery gold film and a second layer of aluminum oxide film. Referring to Figures 4 and 5, comparing sample numbers 40a-40f and 50a-50f, respectively, it can be found that the inverse of Group C (40c and 50c) 9 201022461 has a lower rate of incidence and the cutoff wavelength occurs at a longer wavelength of 1400 nm. Therefore, its absorption rate is also better. In subsequent studies, different nitriding atmosphere concentrations and different film thicknesses can be used to match and find a single-layer absorbing film with a cut-off wavelength at 1600 nm. Compare the best-performing Group C in Figures 4 and 5 and redraw it as shown in Figure 6. Among them, in the single and double-layer film reflectivity, the second film has a tendency to move in the long wavelength direction, and the overall reflectance tends to decrease, so the absorption rate of the double film is 0.8% than that of the single layer film. high. Therefore, in the embodiment of the present invention, a high absorption rate of 0.75 ' can be achieved by selecting a suitable single-layer absorption film, and the single-layer absorption film has selective characteristics, and has high absorption in visible light and near-infrared light regions, and Reflective properties in the far infrared region. § It is naturally heated and oxidized by being placed in the atmosphere, and naturally forms a thin layer of oxide film, which can achieve anti-reflection effect and enhance the absorption efficiency of the selective absorption film. In the current embodiment simulation, in addition to the selective characteristics, the absorption rate can reach 0.8. Sputtering Preparation Sputtering experiments were carried out to prepare a series of cermet films of different nitriding degrees, and at the same time to understand the properties of the single-layer selective absorbing film, and to actually expose the oxidized (aging). First, 12 pieces of metal aluminum film were plated as an A1 substrate, and two A1 substrates and one glass substrate were placed under each different atmosphere sputtering conditions. After the sputtering is completed, the film on the A1 substrate is measured for reflectance, emissivity, and absorptivity. The film on the glass substrate was analyzed for optical constants and film thickness by an ellipsometer. Table 4 shows the parameters of the coating experiment. The sputtering pressure is about 2 mtorr, the Ar flow rate is fixed at 40 sccm, the nitrogen flow rate is 〇-4 sccm, and the sputtering power is 150 W, and plating is performed for 10 minutes. 10 201022461
表4、鍍膜實驗之製程參數 \\^樣品編號 AO A1 A2 A3 A4 濺鍍參數 功率 150 150 150 150 150 (W) 反應氣氛比N2/Ar 0/40 1/40 2/40 3/40 4/40 seem ratio 時間 IQ 10 10 10 10 min 根據陶金鋁膜之顏色外觀，兩組膜之鍍製條件完全相 同僅基板不同，分別為陶金鋁膜鍍製於金屬鋁膜上凡二陶 金鋁膜鍍製於透明玻螭基材上。在通入氮氣之後薄膜則不 似純鋁膜為銀色而呈現褐色。Table 4, process parameters of coating experiment \\^ sample number AO A1 A2 A3 A4 sputtering parameter power 150 150 150 150 150 (W) reaction atmosphere ratio N2/Ar 0/40 1/40 2/40 3/40 4/ 40 seem ratio time IQ 10 10 10 10 min According to the color appearance of the gold film of Taojin, the plating conditions of the two films are exactly the same, only the substrate is different, respectively, the gold-plated aluminum film is plated on the metal aluminum film, and the second ceramic gold-aluminum The film is plated on a transparent glass substrate. The film did not appear as a silvery brown color after passing nitrogen.
第7圖顯示陶金鋁膜鍍於金屬鋁膜上之反射光譜（實 心）’以及放置15天㈣狀反射光譜（空外以樣品曰編號 A3、Α4具有較佳之吸收率，又因為人3之截止波長位置較 長，故吸收率較高為0.771。第8圖係顯示陶金鋁膜鍍於透 明玻璃基材上之穿透光譜（實心），以及放置15天後薄膜之 牙透光譜（空心）。由第7和8圖中的結果得知，薄膜放置 15天後其穿透率及反射率皆有變化，顯示薄膜表面或是薄 膜結構已產生變化，故其吸收率及放射率也有所改變，如 表5所示。吸收率皆有小幅度的增加，Α3試片之吸收率更 同達0.785，唯獨Α4試片之吸收率下降，由第7圖的反射 圖譜即可發現是因為放置15天後其反射圖譜有上升趨勢 .201022461 所致。在放射率部分變動不大，皆為1%幅度之變化，且均 在0.1以下。 以上之模擬與實際鍍膜之實施例，都驗證了單層吸收 膜經曝曬後，可提高吸收膜之吸收率效能。未來，若將實 際鍍膜搭配光學模擬設計，將可製備更關鍵之合適單膜 層，使吸收率（〇〇達Q.8以上。 表5比〗 交吸收膜放置15天前後其效能之差異 ^效能 樣品編 吸收率(α) 吸收率(〇〇 15天後 放射率⑻ 放射率(ε) 15天後 A0 0.083 0.098 0.03 0.02 A1 0.558 0.575 0.08 0.09 A2 0.619 0.646 0.06 0.07 A3 0.771 0.785 0.02 0.03 A4 0.755 0.715 0.02 0.02 本發明雖以較佳實施例揭露如上，然其並非用以限定 本發明的範圍，任何所屬技術領域中具有通常知識者，在 _ 不脫離本發明之精神和範圍内，當可做些許的更動與潤 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。 12 .201022461 【圖式簡單說明】 第1圖係顯示傳統多層選擇性吸收膜結構製作於金屬 基材的剖面示意圖。 第2A-2C圖係顯示根據本發明之一實施例的太陽能選 擇性吸收膜製造方法的剖面示意圖。 第3圖係顯示本發明實施例的光學模擬步驟，並對應 以第2A-2C圖貫施的流程不意圖。 第4與5圖分別顯示根據本發明實施例在不同氮化程 • 度下的單、雙層膜的反射光譜示意圖，其中單層膜為不同 金屬分率之鋁陶金單層膜，雙層膜分別為第一層的鋁陶金 膜及第二層的氧化鋁膜。 第6圖係顯示比較第4與5圖中效果最好的C組，並 重新繪製的反射光譜示意圖。 第7圖顯示陶金鋁膜鍍於金屬鋁膜上之反射光譜（實 心），以及放置15天後薄膜之反射光譜（空心）。 第8圖係顯示陶金鋁膜鍍於透明玻璃基材上之穿透光 參譜（實心），以及放置15天後薄膜之穿透光譜（空心）。 【主要元件符號說明】 習知部分（第1圖） 100〜金屬基材； 110-130〜多層吸收膜結構。 本案部分(第2A~8圖） 200〜基材； ]3 .201022461 210〜單層金屬-陶瓷複合膜； 215〜氧化物薄層； 310-330〜光學模擬步驟； L〜自然大氣下曝曬； 4〇a-40f和50a-50f〜樣品編號。Figure 7 shows the reflection spectrum (solid) of the gold-plated aluminum film on the metal aluminum film and the 15 day (four)-like reflection spectrum (the sample with the sample number A3, Α4 has a better absorption rate, and because of the human 3 The cutoff wavelength is longer, so the absorption rate is higher at 0.771. Figure 8 shows the penetration spectrum (solid) of the gold-plated aluminum film on a transparent glass substrate, and the tooth-permeability spectrum of the film after 15 days of placement (hollow) From the results in Figures 7 and 8, it is known that the transmittance and reflectance of the film change after 15 days of display, indicating that the surface of the film or the structure of the film has changed, so the absorption rate and emissivity are also The change is shown in Table 5. The absorption rate has a small increase, and the absorption rate of the Α3 test piece is more than 0.785. The absorption rate of the 试4 test piece is decreased. The reflection spectrum of Fig. 7 can be found because After 15 days of standing, the reflection spectrum has an upward trend. 201022461. The change in the emissivity is not large, and the change is 1% amplitude, and both are below 0.1. The above simulation and actual coating examples have been verified. After the single layer absorption film is exposed to sunlight, Absorption efficiency of high-absorption film. In the future, if the actual coating is matched with optical simulation design, a more suitable single film layer can be prepared to make the absorption rate (QD8 or higher. Table 5 ratio) Difference in efficacy before and after 15 days^Efficiency sample absorption rate (α) Absorption rate (〇〇15 days post-emissivity (8) Emissivity (ε) After 15 days A0 0.083 0.098 0.03 0.02 A1 0.558 0.575 0.08 0.09 A2 0.619 0.646 0.06 0.07 A3 0.771 0.785 0.02 0.03 A4 0.755 0.715 0.02 0.02 The present invention has been disclosed in the above preferred embodiments, but it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art, without departing from the spirit of the invention In the scope of the invention, the scope of protection of the present invention is defined by the scope of the appended claims. 12 .201022461 [Simple description of the drawings] Figure 1 shows the traditional multi-layer selection A cross-sectional view of a structure of a absorbing film formed on a metal substrate. 2A-2C is a view showing a method of manufacturing a solar selective absorbing film according to an embodiment of the present invention. Fig. 3 is a schematic view showing the optical simulation steps of the embodiment of the present invention, and corresponds to the flow of the second embodiment. Figs. 4 and 5 respectively show different nitriding processes according to an embodiment of the present invention. Schematic diagram of the reflection spectrum of single and double-layer membranes, wherein the single-layer membrane is an aluminum-ceramic single-layer membrane with different metal fractions, and the two-layer membrane is the first layer of aluminum ceramic gold film and the second layer of aluminum oxide, respectively. Fig. 6 is a schematic diagram showing the reflection spectrum of the best-performing group C in Figures 4 and 5 and redrawing. Fig. 7 shows the reflection spectrum (solid) of the gold-plated aluminum film on the metal aluminum film, and the reflection spectrum (hollow) of the film after 15 days of standing. Figure 8 shows the penetration of the ceramic gold film on a transparent glass substrate (solid) and the breakthrough spectrum (hollow) of the film after 15 days of placement. [Main component symbol description] Conventional part (Fig. 1) 100~ metal substrate; 110-130~ multilayer absorption film structure. Part of this case (Fig. 2A-8) 200~substrate; ]3.201022461 210~single layer metal-ceramic composite film; 215~ oxide thin layer; 310-330~ optical simulation step; L~ natural atmospheric exposure; 4〇a-40f and 50a-50f~ sample number.
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