200521521 圍 (發明說明應敘明:發明所屬之技術領域、先前技術、内容、實施方式及 圖式簡單說明） 【發明所屬之技術領域】 本專利發明所屬之技術領域為光學、電機、半導體、感測、生物技術以及 分析與化學等各別與整合領域。 【先前技術】 科學家常希望藉由物質來改變光的行為，如偏光、電激發光、光學導 波等方法將其應用在諸如液晶顯示器、發光二極體、光纖通訊……等等光 電子領域來達到對光的進一步應用。上述的方法大部分是利用改變物質分 子内在化學結構的特性來達成光應用的目的。相對地，由於光波在物質中 具有電磁的特性因此也可以藉由特定物理結構的改變來達到光波長在尺度 上(lOOnrn〜μιη)的應用。 1987 年，Ε· Yablonovitch (Phys· Rev· Lett. 58, 2059, 1987)和 S. John (Phys· Rev· Lett· 58, 2487,1987)不約而同地指出具有電磁波波長尺度之高 度週期性排列之物質，由於該物質具有類比於電子物質波(De-Brogiewave) 與原子晶格大小的特性，電磁波在此巨觀高度次序排列的物質中之行為將 如同電子在晶體中傳送之情形，因此不需要改變物質的内在化學結構，僅 需藉由控制物質空間結構、介電常數和排列週期等參數的改變，即可在電 磁波的波長尺度下設計並製造出我們想要的光的特性，這種具有高度週期 丨门繪次wl 200521521 性排列的介電質結構，因其週期性結構之緣故，導致電磁波通過晶體時由 於反射波對入射波造成干涉，發生所謂的頻溝現象(Bandgap)，阻擋在某些 頻率振盪之電磁波通過因此可形成一種光子的絕緣體，科學家們將這種新 型的材料稱之為光子晶體(photonic crystals)。 光子晶體的基本架構可分為一維、二維或三維光子晶體。一維光子晶 體即是一般所謂的光學多層膜，它已被廣泛用在光分析儀器或是光學鏡片 上，一維光子晶體的應用原理是藉由一維週期排列的多層介質膜造成光子 能隙，促使特定波長的光波無法通過，產生極高的反射效率而達到其應用 的目的。目前最受到重視的是具有二維、三維高度週期性排列結構的光子 晶體，其可能的應用領域眾多，例如藉由在光子晶體中製造一瑕疵區域可 製造出特定光波長的光子共振器，這種共振器的應用原理是藉由光子晶體 結構的控制來限制住某些特定波長的光使其無法穿越此光子絕緣晶體，促 使這些特定波長的光子被限制在此瑕疵區域中，漸漸形成一具有高能量密 度的光子共振場，由於此種光子共振器因為對特定光波長具有選擇性，因 此可以將其應用在光通訊領域中的濾波器件沉）。同時若此 光子共振器的瑕疲區域具有p〇pUlationhversj〇n的特性，則可製造出一具有 零臨界電壓的理想雷射。 此外若在光子晶體巾製造-瑕絲，使特定級長僅能在此瑕絲上 傳導’則可達縣學的顧。但在—般傳統的光學祕光電子元件中， 多是製造-分別含有高與低折神的材料，賴低折射輕域與高折射率 「Π縝次酉] 200521521 區域介質之間的全反射性質’將光侷限在高折射率介質巾使之不散開以便 進行光傳導，由於此材料僅利用材質折射率間的差異來達到光傳導的目 的，因此在使用上對於光的色散效應、可彎曲程度、能量傳遞等方面仍存 有極大的缺陷。相對於傳統全反射式的光波導，若利用光子晶體具有光子 能隙結構的特質，在光子晶體中製造一瑕疵線來作為光波導可使光波被迫 僅能在此波導中前進。這種光波導由於是利用結構的改變來達成，因此可 以使光波在折射率低如空氣的環境下進行傳播，此外若同時藉由光波導的 設計更可以使光波在光子晶體内以僅有極少的能量損失情形而達到大於 90°轉彎方面的應用。這種有別於傳統光纖受限於高折射率光學波導介質的 新型光子晶體波導，其具有很多很重要的應用，尤其是在以光子晶體光波 導取代傳統光纖來作為積體光學元件與光通訊通路方面，更是具有極大的 商業價值。 在二維光子晶艘的研究領域中已經發表的文獻眾多，但多以利用光餘 刻技術來達成，諸如Krauss，T· F等人在1996年的自然（Nature)期刊中所 發表利用近紅外線的光蝕刻技術可以成功的製備出二維結構具有特定光能 隙之光子晶體（Two-dimensional photonic-bandgap structures operating at near-infrared wavelengths·論383, 699-702, 1996)以及 Lin，S· Υ·等人在 1998年科學（Science)期刊中指出利用電磁波的蝕刻技術來製造出具有光 波導特性的光子晶體（Experimental demonstration of guiding and bending of electromagnetic waves in a photonic crystals. ⑼282, 274-276, 1998 )。此 200521521 外，Scherer, A.等人亦在1999年時於科學期刊中提出利用雷射光的蝕刻亦 可製造出具有特定光能隙之光子晶體（Two-dimensional photcmie band_gap defect model laser· 284, 1819_1821(1999)。在專利方面則有美國專利 2002167984 (US2002167984)利用結合不同波長的光源來蝕刻出具有光學 波導的光子晶體。上述的文獻皆是以光钕刻技術來製備二維的光子晶體。 近年來用來製造三維光子晶體所發表的方法眾多，但多是利用光蝕刻 技術以及無機或是有機高分子均一粒徑顆粒的自組裝排列來生成三維光子 晶體。在光蝕刻技術方面所發表的相關文章眾多，在科學文獻方面如：Lin， S. Υ·等人在1998年自然期刊中登錄利用近紅外線的餘刻技術來製造三維 光子晶體（A three-dimensional photonic crystal operating at infrared wavelengths·油rmre 394, 251-253, 1998)以及 2000 年科學期刊中 Noda，S. 等人亦利用近紅外線的蝕刻技術製造出具有光波導特性之三維光子晶體 (Full three-dimensional photonic bandgap crystals at near-infrared wavelengths. &㈣ce 289, 604-606, 2000)。雖然藉由光源與光罩設計已可以 精確的製造出三維光子晶體，但是其製程煩瑣且製作成本高再加上厚度上 無法達到較多層數的限制，因此在應用上仍有極大的限制。 反觀利用無機或是有機高分子均一粒徑顆粒進行諸如沈澱、離心、揮 發以及傾斜等方式來達到均一粒徑顆粒自組裝模式所生成的光子晶體則是 目前主要的研究方向，如Vlasov，Y. A.等人在2001年自然期刊（On-chip natural assembly of silicon photonic bandgap crystals. Nature 414, 289-293, 200521521 2001)中發表利用緩慢提升矽基材的方式可將二氧化矽均一粒徑顆粒附著 在機材表面而生成光子晶體，但在此製程中由於提升基材的速度極慢且所 生成的光子晶體厚度亦只能達數個微米，因此尚無法應用於工業製程上。 此外科學家亦利用添加金屬烷氧化物於三維光子晶體中，再藉由溶劑 萃取或是鍛燒等方式將光子晶體移除，最後獲得具有三維結構的轉錄 (inverse)光子晶體，如Holland, B.T·等人於1998年發表於科學期刊中 (Synthesis of macroporous minerals with highly ordered three-dimensional arrays of spheroidal voids. 5W⑽281，538-540, 1998)以真空抽濾的方式先 製備出聚苯乙稀均一粒徑顆粒光子晶體，再於其上添加金屬烧氧化物最後 再以尚溫鍛燒的形式將有機物移除而得轉錄光子晶艘，其結構方面可大大 的增強，相對的應用性也更加寬廣。 此外由於光子晶體是屬於科學界極新的研究，因此根據近年來在不同 領域研究的科學家的研究判斷，光子晶體可以廣泛的應用在光通訊、光波 導光開關、雷射、全反射材料、積鱧光路、負折射、量子電腦、濾波器、 生醫（細胞培養·人工器官·生物分離技術）、感測器、儲能材料、表面塗佈、 光學照明、背光模組、光子染料、管柱層析儀填充吸附材、半導體製程以 及未來取代現今電腦之光腦等領域。 但現今製造光子晶體的製法多耗時且複雜，因此製程方面仍有改善的 空間。 □續次頁 200521521 【内容】 本篇專利的特點是在克服現有利用均—粒徑顆粒製造光子 及製法方祕關^專_容由奈微_粒在_巾的觀以及轉 理温度方關控制，在纽__液界喊是_表峡上層快速的生成三 維結構之光子晶體。料顧揮發性溶_添加可以得到不鳴列結構之 光子晶髏。同時若藉由熱處理賴的控制亦可控制三維結構之光子晶體的 厚度 【實施方式】 卜第-®所示為根據本發明製備三縣子晶_流程示意圖。在本專利的 一實施例中’三維光子晶體的製備是利用奈米均一粒徑顆粒在系統的氣-液界面或是液體表面與上層的堆養而達成。在一實施例中該奈米均一粒 徑顆粒的組成可以是一以具未飽和鍵之有機單體聚合而成的，例如:苯乙 烯系列、丙烯酸系列及馬來酸系列……等等系列之材質或是其組合。在 一實施例中該奈米均一粒徑顆粒的組成可以是以含無機與有機成分，碳_ 矽、碳鈇、碳·鍅、碳-铭等等系列之材質或是其組合。在一實施例中該 奈米均一粒徑顆粒的組成可以是以含無機成份之材質所組成的，例如: 矽、鈦、锆、金、銀、鐵、鋁、銅......等金屬或是其組合。 2、實驗例一中選擇含奈米均一粒徑顆粒液體其濃度範圍可介於90%〜0. 時系統酸鹼值介於1〜9時，在40〜150。<：時於氣-液表面與液體上層可 生成光子晶體。 「□續次頁| 200521521 3、 在實驗例二中採用與實驗一所述之製造方式，將奈米苯乙烯球在8〇 〇c 及30%濃度的條件下於一分鐘之内氣_液表面即有光子晶體生成。(圖二) 4、 在實驗例三中採用與實驗一所述之製造方式並添加不同比例之較低沸 點溶液(如乙醇、丙酮)於同實驗例一之系統中可得較鬆散排列之光子晶 體。（圖三） 5、 在實驗例四中於同實驗例一之系統增長其熱處理時間，一小時内光子晶 體的厚度亦可以控制增厚至3〇〇微米以上。 6、 在實關五中闕實驗例—之纽，所·之奈料—粒_粒可以是 同粒徑不同材質、不同粒徑同材質或是不同粒徑不同材質之組合。 7、 在實驗-至六巾可藉由無機㈣(如:麵祕晶元)、錢與織複合材 質與有機材質(如塑膠)等將光子晶體取出。 □續次頁 200521521 【圖式簡單說明】 第-圖所示為根據本發明製備三維光子晶體的流程示意圖。步驟8是奈米 顆粒溶液在自然環境(室溫)中是—穩定絲子晶體的液體。步驟i〇、12、 14、16、18、2G是鱗獅帽讀舰度、濃度、酸雜、添加溶液及 反應時間與奈米顆粒其粒徑組成條件下，光子晶體會在氣液表面與液體上 層生成。步驟26是當系統反應_延長時光子晶_面積與厚度皆會繼續 成長。步驟28是將光子晶體從反應系統移出，即可得到光子晶體產物。 第二圖是苯乙烯球在氣-液表面生成光子晶體。 修 第三圖是添加溶劑可得到不同排列之光子晶體。 第四圖是光子晶體可隨反應時間增加而計增厚增廣。200521521 (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings are briefly explained.) [Technical field to which the invention belongs] The technical fields to which this patent invention belongs are optics, motors, semiconductors, sensors Separate and integrated areas such as measurement, biotechnology, and analysis and chemistry. [Previous technology] Scientists often hope to change the behavior of light through materials, such as polarized light, electrically excited light, optical guided waves, etc., and apply it to optoelectronic fields such as liquid crystal displays, light-emitting diodes, fiber optic communications, and so on. Achieve further application of light. Most of the above methods use the characteristics of the molecular chemical structure of the material to achieve the purpose of light application. In contrast, because light waves have electromagnetic properties in matter, the application of light wavelengths on a scale (100nrn ~ μιη) can also be achieved by changing specific physical structures. In 1987, E. Yablonovitch (Phys · Rev. Lett. 58, 2059, 1987) and S. John (Phys · Rev. Lett 58, 2487, 1987) involuntarily pointed out substances with a highly periodic arrangement of the wavelength scale of electromagnetic waves Since the substance has characteristics similar to the electronic substance wave (De-Brogiewave) and the size of the atomic lattice, the electromagnetic waves will behave as if the electrons are transported in the crystal in this order of macroscopic order, so there is no need to change The intrinsic chemical structure of matter can be designed and manufactured in the wavelength scale of electromagnetic waves only by controlling changes in the material's spatial structure, dielectric constant, and arrangement period. Period 丨 gate drawing wl 200521521 Due to its periodic structure, the electromagnetic wave passes through the crystal and the reflected wave interferes with the incident wave due to the periodic structure. The so-called bandgap phenomenon occurs, blocking in a certain Some electromagnetic waves with frequency oscillation pass through to form a photonic insulator. Scientists call this new type of material a photonic crystal (photonic crystal). crystals). The basic architecture of photonic crystals can be divided into one-dimensional, two-dimensional or three-dimensional photonic crystals. One-dimensional photonic crystals are generally called optical multilayer films. They have been widely used in optical analysis instruments or optical lenses. The application principle of one-dimensional photonic crystals is to create a photon energy gap through a multilayer dielectric film arranged periodically in one dimension. , Promote the specific wavelength of light waves can not pass, resulting in extremely high reflection efficiency to achieve the purpose of its application. At present, the most valued are photonic crystals with a two-dimensional and three-dimensional highly periodic arrangement structure. There are many possible applications. For example, a photon resonator with a specific light wavelength can be manufactured by manufacturing a defective region in a photonic crystal. The application principle of this type of resonator is to control the photonic crystal structure to limit certain wavelengths of light so that they cannot pass through the photonic insulating crystal. This urges these specific wavelengths of photons to be confined in this defective region, and gradually forms a High-energy-density photon resonance field. Because this kind of photon resonator is selective for specific light wavelengths, it can be applied to filter devices in the field of optical communication). At the same time, if the defect region of the photon resonator has the characteristics of pOpUlationhversjon, an ideal laser with zero threshold voltage can be manufactured. In addition, if a flaw is made in a photonic crystal towel so that a specific grade can only conduct on the flaw, it can reach the county school. However, in the traditional optical optoelectronic components, most of them are made of materials that contain high and low refraction, respectively, relying on the total reflection properties between the low-refractive light domain and the high refractive index "Π 缜 次 酉" 200521521 'Limit the light to the high-refractive index towel so that it does not spread out for light transmission. Since this material only uses the difference between the refractive indices of the materials to achieve the purpose of light transmission, it has a dispersion effect on the light and can be bent. There are still great shortcomings in terms of energy transfer, etc. Compared to traditional total reflection optical waveguides, if a photonic crystal has the characteristics of a photonic energy gap structure, a defect line in the photonic crystal can be used as an optical waveguide to make light waves Can only advance in this waveguide. Because this type of optical waveguide is achieved by structural changes, it can make light waves propagate in an environment with a low refractive index, such as air. In addition, the design of the optical waveguide can also make it more The application of light waves in photonic crystals with more than 90 ° turns with very little energy loss. This is different from traditional optical fibers. The new photonic crystal waveguide of the refractive index optical waveguide medium has many very important applications, especially in terms of replacing traditional optical fibers with photonic crystal optical waveguides as integrated optical components and optical communication paths, and has great commercial value. Numerous literatures have been published in the research field of two-dimensional photonic crystal vessels, but they are mostly achieved by the use of photolithography. For example, Krauss, TF and others published in the 1996 Nature journal using near-infrared rays. Photoetching technology can successfully produce two-dimensional photonic crystals with specific optical band gaps (Two-dimensional photonic-bandgap structures operating at near-infrared wavelengths · On 383, 699-702, 1996) and Lin, S · S · In 1998, Science pointed out that the use of electromagnetic wave etching technology to produce photonic crystals with optical waveguide characteristics (Experimental demonstration of guiding and bending of electromagnetic waves in a photonic crystals. ⑼282, 274-276, 1998 ). In addition to 200521521, Scherer, A. and others also proposed in scientific journals in 1999. Photonic crystals with specific optical band gaps (Two-dimensional photcmie band_gap defect model laser · 284, 1819_1821 (1999) can also be produced by laser light etching. In the patent area, there is a US patent 2002167984 (US2002167984) which uses A light source to etch a photonic crystal with an optical waveguide. The above-mentioned documents are all based on photo-neodymium engraving technology to prepare two-dimensional photonic crystals. In recent years, there have been many published methods for manufacturing three-dimensional photonic crystals, but most of them use photo-etching techniques and self-assembled arrangements of particles of uniform size of inorganic or organic polymers to generate three-dimensional photonic crystals. There are many related articles published in photoetching technology. In the scientific literature, such as: Lin, S. Υ ·, etc., registered in the 1998 Nature Journal using the near-infrared etch technology to manufacture three-dimensional photonic crystals. photonic crystal operating at infrared wavelengths, oil rmre 394, 251-253, 1998) and the 2000 scientific journal Noda, S. et al. also used near-infrared etching technology to produce three-dimensional photonic crystals with optical waveguide characteristics (Full three- dimensional photonic bandgap crystals at near-infrared wavelengths. & ㈣ce 289, 604-606, 2000). Although the three-dimensional photonic crystal can be accurately manufactured by the design of the light source and the mask, the process is cumbersome and the manufacturing cost is high. In addition, the thickness cannot reach a large number of layers. Therefore, there are still great limitations in application. In contrast, the use of inorganic or organic polymers with uniform particle size such as precipitation, centrifugation, volatilization, and tilt to achieve uniform particle size self-assembly mode is the current main research direction, such as Vlasov, YA, etc. In the 2001 Nature Journal (On-chip natural assembly of silicon photonic bandgap crystals. Nature 414, 289-293, 200521521 2001), the method of slowly raising the silicon substrate can be used to attach silica particles with uniform particle size to the machine. Photonic crystals are generated on the surface, but in this process, because the speed of raising the substrate is very slow and the thickness of the generated photonic crystals can only reach a few micrometers, it is not yet applicable to industrial processes. In addition, scientists also use metal alkoxides in three-dimensional photonic crystals, and then remove the photonic crystals by solvent extraction or calcination, and finally obtain three-dimensional inverse photonic crystals, such as Holland, BT · Et al. (Synthesis of macroporous minerals with highly ordered three-dimensional arrays of spheroidal voids. 5W⑽281, 538-540, 1998) was first published in scientific journals in 1998 by vacuum filtration. Particle photonic crystals, metal oxides are added to them, and then the organic matter is removed in the form of high temperature calcination to obtain transcription photonic crystal boats. The structure can be greatly enhanced, and the relative applicability is also broader. In addition, since photonic crystals are extremely new research in the scientific community, according to the research judgments of scientists who have studied in different fields in recent years, photonic crystals can be widely used in optical communications, optical waveguide optical switches, lasers, total reflection materials, and products.鳢 Optical path, negative refraction, quantum computer, filter, biomedical (cell culture, artificial organ, bio-separation technology), sensor, energy storage material, surface coating, optical lighting, backlight module, photonic dye, tube string Chromatographs are filled with adsorbent materials, semiconductor processes, and optical brains that will replace today's computers. However, the manufacturing methods of manufacturing photonic crystals today are time-consuming and complicated, so there is still room for improvement in the manufacturing process. □ Continued on page 200521521 [Content] The feature of this patent is to overcome the existing secrets of using the average-size particles to make photons and the method of making them ^ Special_Rongyou Nano_Pellet_ View of the towel and the control of the temperature control In the New York __Liquid World Shout is _ the upper layer of the Table Gorge to quickly generate a three-dimensional photonic crystal. Expect volatile solvents_addition can get the photonic crystal structure of the unlisted structure. At the same time, the thickness of the three-dimensional photonic crystal can also be controlled by the control of the heat treatment. [Embodiment] Budi-® shows a schematic diagram of the process of preparing three-country crystals according to the present invention. In one embodiment of the present invention, the preparation of the 'three-dimensional photonic crystal is achieved by using nano-sized particles of uniform size at the gas-liquid interface of the system or the liquid surface and the upper layer. In one embodiment, the composition of the nano-sized particles may be polymerized by an organic monomer having an unsaturated bond, such as: styrene series, acrylic series, maleic acid series, etc. Materials or a combination of them. In an embodiment, the composition of the nano-sized particles can be made of materials including inorganic and organic components, carbon-silicon, carbon hafnium, carbon hafnium, carbon-ming, etc., or a combination thereof. In one embodiment, the composition of the nano-sized particles may be composed of materials containing inorganic components, such as silicon, titanium, zirconium, gold, silver, iron, aluminum, copper, etc. Metal or a combination. 2. In Experimental Example 1, a liquid containing nano particles with a uniform particle size was selected, and its concentration range could be between 90% and 0. When the system pH was between 1 and 9, it was between 40 and 150. <: Photonic crystals can be formed on the gas-liquid surface and the upper layer of the liquid. "Continued on the next page | 200521521 3. In the second example, the manufacturing method described in the first experiment was adopted. The nano-styrene spheres were aerated within one minute under the conditions of 800 ° C and 30% concentration. Photonic crystals are formed on the surface. (Figure 2) 4. In Experiment 3, the manufacturing method described in Experiment 1 was used, and a lower boiling point solution (such as ethanol and acetone) was added to the system in Experiment 1 A loosely arranged photonic crystal can be obtained. (Figure 3) 5. In Experimental Example 4, the heat treatment time is increased in the same system as Experimental Example 1. The thickness of the photonic crystal can be controlled to increase to more than 300 microns in one hour. 6. In the practical example of the 5th Middle School, the experimental example—Zhong, So Nai—Materials—The grains can be made of different materials with the same particle size, the same material with different particle sizes, or a combination of different materials with different particle sizes. Experiment-To six towels, the photonic crystals can be taken out by inorganic rhenium (such as facet crystals), money and weaving composite materials and organic materials (such as plastic). □ Continued on page 200521521 [Schematic description] Section- The figure shows the process of preparing a three-dimensional photonic crystal according to the present invention. Schematic diagram. Step 8 is the nano particle solution in the natural environment (room temperature)-a liquid that stabilizes silk crystals. Steps i0, 12, 14, 16, 18, 2G are reading scales, concentrations, acids Under the conditions of impurity, addition solution, reaction time and nanometer particle size composition, photonic crystals will be formed on the gas-liquid surface and the upper layer of the liquid. Step 26 is that the area and thickness of photonic crystals will continue to grow when the system reacts_extends. Step 28 is to remove the photonic crystal from the reaction system, and the photonic crystal product can be obtained. The second picture is a styrene ball forming a photonic crystal on the gas-liquid surface. The third picture is the addition of a solvent to obtain photonic crystals with different arrangements. The fourth figure shows that the photonic crystal can be thickened and enlarged with the increase of the reaction time.
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