TW533228B

TW533228B - Hardcoats for flat panel display substrates

Info

Publication number: TW533228B
Application number: TW88112697A
Authority: TW
Inventors: Chandra Venkatraman; Cyndi L Brodbeck
Original assignee: Advanced Refractory Tech
Priority date: 1998-07-27
Filing date: 1999-07-27
Publication date: 2003-05-21
Also published as: AU5326499A; EP1109947A1; EP1109947A4; JP2002521247A; WO2000006794A9; WO2000006794A1

Abstract

The present invention relates to a unique hard coating that provides the necessary characteristics for flat panel display plastic substrates because the coating is amorphous and is comprised of C, H, Si and O. The coating of the present invention is hard, optically transparent, scratch and abrasion resistant and hydrophobic. It is deposited by a low density, low temperature plasma enhanced chemical vapor deposition (PECVD) process and exhibits excellent barrier protection and reduced permeability to moisture, oxygen, helium and other vapors.

Description

533228 五、發明說明（1) 明範圍本發明通常係關於平面顯示器塑膠基板上之透明硬質塗層。更特別地，本發明係關於一種由碳，氫，石夕和氧所組成之塗層。發明背景平面顯示器（FPD)擁有廣泛消費者，工業上和軍事上之應用，且在2000年之前計畫超過美金二億元。在許多FPD 技術形式中，液晶顯示器（LCD)技術帶頭且最成熟。在 L C D市場中由於市場改變，利潤餘逐漸變低。在逐漸迫切降低製造F P D之材料成本，其估計約為顯示器總成本之 4 0至5 0 %。存在尋找新I員材料，減輕重量，減低顯示器厚度，改良觀看角度和降低背光之趨勢。對於製造下一代一個重要挑戰，係以塑膠顯示器取代玻璃顯示器。塑膠顯示器重量較輕，具抗碎性且能夠提供與玻璃相等之透射性質。然而，如聚碳酸酯和聚對酞酸二甲酯（PET)之塑膠並不抗碎與抗磨。重要的是提供塑膠硬質塗層，以具備良好透射和符合有效作為平面顯示器之折射率。塑膠之另一缺點在於可滲透液體和蒸氣，其是不希望得到的。滲透水蒸氣，氧，液晶和其它氣體可能破壞平面顯示器後之電子裝置，倘若未提供適當阻擋保護。因此該硬質塗層亦需要不可滲透液體，蒸氣和製造FPD時使用之溶劑。塑膠基板FPD之市場相當大，以LCD市場最傑出。塑膠基板顯示器能夠用於LCD應用，其近來係使用鹼石灰玻璃顯533228 V. Description of the invention (1) Scope of the invention The present invention generally relates to a transparent hard coating on a plastic substrate of a flat panel display. More specifically, the present invention relates to a coating composed of carbon, hydrogen, stone and oxygen. BACKGROUND OF THE INVENTION Flat panel displays (FPDs) have a wide range of consumer, industrial and military applications, and plans to exceed $ 200 million by 2000. Among many FPD technology forms, liquid crystal display (LCD) technology is leading and the most mature. In the L C D market, due to market changes, profit margins have gradually become lower. It is urgent to gradually reduce the material cost of manufacturing F P D, which is estimated to be about 40 to 50% of the total cost of the display. There is a tendency to find new members, reduce weight, reduce display thickness, improve viewing angle, and reduce backlight. An important challenge for manufacturing the next generation is replacing glass displays with plastic displays. Plastic displays are lightweight, shatter-resistant and provide transmission properties equivalent to glass. However, plastics such as polycarbonate and poly (dimethyl terephthalate) (PET) are not resistant to chipping and abrasion. It is important to provide a hard plastic coating to provide good transmission and conform to the refractive index effective as a flat panel display. Another disadvantage of plastic is that it is permeable to liquids and vapors, which is undesirable. Permeation of water vapor, oxygen, liquid crystals, and other gases may damage electronic devices behind the flat panel display if proper barrier protection is not provided. Therefore, the hard coating also requires impermeable liquids, vapors, and solvents used in the manufacture of FPDs. The market for plastic substrate FPD is quite large, and the LCD market is the most outstanding. Plastic-based displays can be used in LCD applications, which recently used soda-lime glass displays

第5頁 533228 五、發明說明（2) 示器。這是夠在如五千質塗佈塑膠機，遊戲機錄器，照相溫度計，工工業上存料之主要塗由碳和鼠組喷霧或浸潰浸塗，為塗佈加工需易燃，由於高沉積速率作，且具環本發明係乙二酯之熱超過7 0 °C。度能夠維持質塗層之間 (如2 0 0 °C痛史個問題。本積，毫米而Page 5 533228 5. Description of the invention (2) indicator. This is enough to coat the main coatings such as five thousand quality coated plastic machines, game recorders, photo thermometers, industrial and industrial coatings by carbon and rat spray or dip dip coating, which is flammable for coating processing. Due to the high deposition rate, and the heat of the ethylene glycol of the present invention exceeds 70 ° C. The degree of maintenance can be maintained between the quality coatings (such as 200 ° C pain history problems. The volume, mm and

Itb 顯示萬平顯示，個機，業顯在許層為成，，接濕式要數顧及沉積保性一種敏性然而在室不存高）發明浸塗器市場相當大的一個部份且在2 0 0 0年前能方英吋般高。LCD應用，其中能夠使用硬器，包括消費者應用，如鐘，錶，計算人數位助手（P D A )，電話，電視，攝像記且工業應用包括PC，醫藥設備，傳真機，示器，測試設備等等。多硬質塗料可以使用。可以認定為硬質塗 DLC和聚矽氧烷浸潰塗料。傳統之DLC塗料無矽和氧。聚矽氧烷塗料係以旋轉塗佈，著熟化步驟或U V硬化而沉積。化學加工，其需要重要的操作處理且完成小時。同時，使用之化學品部份具毒性且環保而使其逐漸難以操作。本發明具有以塗層之潛力，其具成本效益，需要最少操低溫法’能夠在例如聚^酸§旨和聚對駄酸塑膠上沉積。正常操作期間，基板溫度不，能夠將基板溫度活動性冷卻，且基板溫溫。因為本發明涉及低溫法，在基板和硬在熱失配結果。D L C法典型上需要較高溫，因而採用DLC技術塗佈低溫材料顯然是一能夠在如0. 0 7 5毫米般薄之基板材料上沉聚矽氧烷法則需要硬質基板（最小厚度〜1Itb display Wan Ping shows that the machine is very successful in the layer, and the wet type must take into account the sensitivity of the deposit, but it is not high in the room.) The invention of the dip coating device market is quite a large part and in 2 0 0 0 years ago can be as high as an inch. LCD applications where hardware can be used, including consumer applications such as clocks, watches, personal digital assistants (PDAs), telephones, televisions, video cameras, and industrial applications including PCs, medical equipment, fax machines, displays, test equipment and many more. Multiple hard coatings can be used. Can be identified as hard coating DLC and polysiloxane dip coating. Traditional DLC coatings are free of silicon and oxygen. Polysiloxane coatings are deposited by spin coating, curing or UV curing. Chemical processing, which requires significant operational processing and is completed in hours. At the same time, some of the chemicals used are toxic and environmentally friendly, making them difficult to handle. The present invention has the potential for coatings, which are cost-effective and require minimal manipulation of low temperature processes' to be able to be deposited on, for example, polyacids and polyparaisocyanates. During normal operation, the substrate temperature is not high enough to cool the substrate temperature and the substrate temperature. Because the present invention relates to a low temperature method, the substrate and hard thermal mismatch result. The DLC method typically requires a higher temperature, so applying DLC technology to coat low-temperature materials is obviously a method capable of sinking on a substrate material as thin as 0.05 mm. The polysiloxane method requires a hard substrate (minimum thickness ~ 1

第6頁 533228 五、發明說明（3) DLC塗層呈現高壓縮硬力（常為本發明之5倍），產生對於基板之不良黏附。D L C之不良黏附需要使用内層以改良黏附，其於本發明中不需要。本發明產生一種相對於聚矽氧烷浸塗為非常硬質之塗層。該聚矽氧烷塗層不如玻璃般抗磨。DLC塗層較本發明硬，但因為硬度提高，其呈現提高之内部應力，因而需要内層以促進黏附。佩密西（Petrmichl) et al (美國專利第5，618，619號）討論一種使用離子輔助法沉積之抗磨塗層，微壓痕硬度為 2至約5 G P a。佩密西e t a 1之塗層較本發明軟，且其作為阻擋塗層之效益未知。佩密西et a 1 之發明亦教導僅使用矽氧烷或矽烷和氧。此限制能夠達到之最高塗層硬度。在本發明中除了氧和矽氧烷或矽烷先質外使用氫是新穎的，且使得能夠達到更高硬度。佩密西e t a 1未指出材料中在 C，Η，S 1和0間之鍵結本質。諳熟材料科學和工程者熟知這些塗層間之鍵結影響材料之性質。林恩（L 1 n ) e t a 11頃提出使用矽氧烷和氧作為先質材料，以高強度微波電子迴旋加速器共振放電沉積S i 02狀薄膜。產生之塗層材料與本發明不同，且主要由二氧化矽組成。傅立葉變換紅外光譜計（FT I R )指出存在S 1 02狀帶 (朝向較高波數和較尖銳之S i - 0伸長）和少量S i - C Η 3鍵結。由林恩e t a 1使用之高強度等離子體研究可能成為在薄膜中觀察到不同形式鍵結，不同材料密度（存在微孔）和較高氧濃度之原因。即使林恩e t a 1未提出阻擋性質，預Page 6 533228 V. Description of the invention (3) The DLC coating exhibits high compressive hard force (often 5 times that of the present invention), resulting in poor adhesion to the substrate. The poor adhesion of D L C requires the use of an inner layer to improve adhesion, which is not required in the present invention. The present invention produces a coating that is very hard relative to polysiloxane dip coating. The polysiloxane coating is not as abrasion resistant as glass. The DLC coating is harder than the present invention, but because of the increased hardness, it exhibits increased internal stress, and therefore requires an inner layer to promote adhesion. Petrmichl et al (U.S. Patent No. 5,618,619) discuss an anti-wear coating deposited using an ion-assisted method with a micro-indentation hardness of 2 to about 5 G Pa. The coating of Permise e t a 1 is softer than the present invention, and its benefits as a barrier coating are unknown. The invention of Permise et a 1 also teaches the use of only siloxanes or silanes and oxygen. The highest coating hardness this limit can achieve. The use of hydrogen in addition to oxygen and the siloxane or siloxane precursor in the present invention is novel and enables higher hardness to be achieved. Permisi e t a 1 does not indicate the nature of the bond between C, Η, S 1 and 0 in the material. Familiar materials science and engineers are well aware that the bond between these coatings affects the properties of the material. Lynn (L 1 n) e t a 11 proposes the use of siloxane and oxygen as precursor materials to deposit Si 02 films with high-intensity microwave electron cyclotron resonance discharge. The resulting coating material is different from the present invention and consists mainly of silicon dioxide. A Fourier transform infrared spectrometer (FT I R) indicates the presence of S 1 02 bands (towards higher wavenumbers and sharper Si-0 elongation) and a small amount of Si-C Η 3 bonds. The high-intensity plasma research used by Lynn e t a 1 may be the reason for the observation of different forms of bonding, different material densities (micropores), and higher oxygen concentrations in the film. Even if Lynn e t a 1 does not propose blocking properties,

第7頁 533228 五、發明說明（4) 期微孔塗層具有不良阻擋性質。此材料之硬度範圍未知。多夫曼（Dorfman) et al(美國專利第5，466，431和 5，3 5 2，4 9 3號）敘述一種由C，Η，S i和0組成之鑽石狀塗層。多夫曼et al塗層在紫外-可見範圍内之透光性受限，且非常取決於塗層厚度。因此，多夫曼et al之塗層不具有於同本發明之塗層之相同透明度。因此，工業上需要一種用於塑膠基板，更明確地係用於平面顯示器之塗層，其能夠以高沉積速率以低溫法沉積在塑膠基板上；其具經濟效益，且具環保性；且其產生一種硬質，透光，不可滲透，抗碎，抗磨且並具有良好黏附之塗佈產物。發明摘要本發明係關於一種獨特之之硬質塗層，其能夠提供平面塑膠基板必需之特徵。該塗層為非晶形且由C’ H’ Si和〇組成。本發明之塗層為硬質，透光，不可滲透，抗碎，抗磨且係以低強度之低溫等離子體強化化學蒸氣沉積 (PEC VD )法沉積。本發明之塗層係在低溫（低於7 (TC )沉積’且頃成功地沉積在例如聚碳酸§旨’聚對敝酸乙二S旨 (PET)，聚乙稀，氟聚合物和其類似物之透明塑膠上。除了以上優點外，本發明之塗層呈現優良阻擋保護。該塗層為無孔，且呈現降低之濕氣，氧，氦和其它蒸氣之滲透性。該塗層為疏水性（撥水且避免潮濕），其產生改良之阻擋保護。本發明之目的在於提供塑膠基板一種具有適當性質之塗Page 7 533228 V. Description of the invention (4) The microporous coating has poor barrier properties. The hardness range of this material is unknown. Dorfman et al (U.S. Pat. Nos. 5,466,431 and 5,3 52, 4 93) describe a diamond-like coating composed of C, Η, Si, and 0. Doffman et al coatings have limited light transmission in the UV-visible range and are very dependent on the thickness of the coating. Therefore, the coating of Doffman et al does not have the same transparency as the coating of the present invention. Therefore, there is a need in the industry for a coating for a plastic substrate, more specifically a flat display, which can be deposited on a plastic substrate at a high deposition rate and a low temperature method; it is economical and environmentally friendly; and Produces a hard, light-transmissive, impermeable, shatter-resistant, abrasion-resistant, and well-adhesive coated product. Summary of the Invention The present invention relates to a unique hard coating that can provide the necessary characteristics of a flat plastic substrate. The coating is amorphous and consists of C 'H' Si and 〇. The coating of the present invention is hard, light-transmissive, impermeable, shatter-resistant, and wear-resistant, and is deposited by a low-intensity low-temperature plasma-enhanced chemical vapor deposition (PEC VD) method. The coatings of the present invention are deposited at low temperatures (less than 7 (TC)) and have been successfully deposited on, for example, polycarbonate § aim 'Polyethylene terephthalate (PET), polyethylene, fluoropolymer and others Analog transparent plastic. In addition to the above advantages, the coating of the present invention exhibits excellent barrier protection. The coating is non-porous and exhibits reduced permeability to moisture, oxygen, helium and other vapors. The coating is Hydrophobicity (water repellency and avoiding moisture), which results in improved barrier protection. The object of the present invention is to provide a plastic substrate with a coating having suitable properties.

第8頁 533228 五、發明說明（5) ^L· 〇本發明之另一目的在於提供塑膠基板一種能夠在低於7 0 °C沉積之塗層，因而使其能夠適當地塗佈各種彈性基板材料。本發明之進一步目的在於提供塑膠基板一種塗層，其具有優良黏附，高硬度，在可見和紅外波長内之優良透射，低薄膜應力，高度環境穩定性，低表面能量和高水接觸角。而本發明之另一目的在於提供塑膠基板一種不滲透濕氣和腐蝕氣體之塗層，因而提供内部電路之保護阻擋。附圖簡述圖1為硬質塗層沉積室概要圖。圖2為塗層與未塗佈聚碳酸酯，裸玻璃和聚矽氧烷浸塗聚碳酸酯之硬度比較。圖3為玻璃上塗層之典型UV -可見透光和反射光譜。發明詳述 .本發明係關於在平面顯示器之透明塑膠基板上使用透明，硬質，抗磨損碳，含氫之塗層。然而，一個本發明塗層之尤其較佳具體實施例包括非晶形結構之碳，氫，矽和氧。此處使用之π非晶形M表示在固態之不規則結構或原子排列，其產生無長範圍之規則順序，且不晶性或粒性。因此，用以塗佈彈性基板之較佳材料，如此所述，可以主要包括一種玻璃狀Si-Ο網路；或一種包括Si-〇，C-H， S i - Η和S i - C之多組份結構。在後者中，主要為S i - 0和Page 8 533228 V. Description of the invention (5) ^ L · 〇 Another object of the present invention is to provide a plastic substrate which can be deposited at a temperature lower than 70 ° C, so that it can properly coat various elastic substrates. material. A further object of the present invention is to provide a coating for a plastic substrate, which has excellent adhesion, high hardness, excellent transmission in visible and infrared wavelengths, low film stress, high environmental stability, low surface energy and high water contact angle. Yet another object of the present invention is to provide a coating of a plastic substrate that is impermeable to moisture and corrosive gases, thereby providing a protective barrier for internal circuits. Brief Description of the Drawings Figure 1 is a schematic view of a hard coating deposition chamber. Figure 2 shows the hardness comparison between coated and uncoated polycarbonate, bare glass, and silicone dip-coated polycarbonate. Figure 3 shows a typical UV-visible transmission and reflection spectrum of a coating on glass. Detailed description of the invention. The present invention relates to the use of a transparent, hard, wear-resistant carbon, hydrogen-containing coating on a transparent plastic substrate of a flat display. However, a particularly preferred embodiment of the coating of the present invention includes an amorphous structure of carbon, hydrogen, silicon, and oxygen. As used herein, π amorphous M represents an irregular structure or atomic arrangement in a solid state, which results in a regular order without a long range, and is amorphous or granular. Therefore, the preferred material for coating the elastic substrate, as described above, may mainly include a glassy Si-O network; or a group consisting of Si-〇, CH, S i-Η and S i-C份结构。 Share structure. In the latter, S i-0 and

第9頁 533228 五、發明說明（6)Page 9 533228 V. Description of the invention (6)

C 其它組份為少量在本發明之較佳鑽石狀塗層中之碳含量大於該塗層之約 2 5原子百分比，較佳為該塗層之約2 5原子百分比至該塗層之約6 5原子百分比。雖然此類塗層理論上可以不具任何氫而製備，該氫含量較佳為至少該塗層之約1原子百分比上至該塗層之約4 0原子百分比。矽含量為該塗層之約1 0原子百分比上至該塗層之約3 0原子百分比，而氧含量為該塗層之約8原子百分比上至該塗層之約4 0原子百分比。塗層之密度在約1 . 7克/ c c至約2. 0克/ c c之間變化。本發明之較佳塗層為經由RF放電等離子體法合成之硬質碳含矽塗層，該法為諳熟薄膜沉積者易於瞭解之一般方法。碳和含矽自由基能夠以等離子體放電並沉積於真空室中施加高伏特電場之基板上而產生。圖1顯示一個用以沉積較佳硬質塗層之塗佈室的較佳具體實施例。提供一真空沉積室1 0 0以塗佈基板樣品。先質入口系統1 1 0，包括一金屬管和氣體分配環，經由該環及環注入液體先質，較佳為低蒸氣壓矽氧烷。先質入口系統 1 1 0經顯示為經由室側壁而導入室1 0 0中。一種替代排列係將先質經由氣體喷頭穿過室頂端1 1 5注入室1 0 0中。將樣品從室115頂部或通過裝載鎖（未示出）裝入室中。該室包括具頂部和底部平行板1 1 7之圓柱包圍。使用能量供應以將電極偏壓（RF-13. 56 MHz)。實務上，使用傳統真空步驟將系統M抽停（pumped down)"。關閉門閥和前置真空管線閥 (未示出），以乾燥氮或氬回填該系統直到該示達到大氣C Other components are small amounts of carbon content in the preferred diamond-like coating of the present invention greater than about 25 atomic percent of the coating, preferably from about 25 atomic percent of the coating to about 6 5 atomic percent. Although such coatings can theoretically be prepared without any hydrogen, the hydrogen content is preferably at least about 1 atomic percent of the coating up to about 40 atomic percent of the coating. The silicon content is from about 10 atomic percent of the coating up to about 30 atomic percent of the coating, and the oxygen content is from about 8 atomic percent of the coating up to about 40 atomic percent of the coating. The density of the coating varies between about 1.7 g / c c to about 2.0 g / c c. The preferred coating of the present invention is a hard carbon silicon-containing coating synthesized by the RF discharge plasma method, which is a general method that is readily understood by those skilled in film deposition. Carbon and silicon-containing radicals can be generated by plasma discharge and deposition on a substrate in a vacuum chamber with a high-volt electric field applied. Figure 1 shows a preferred embodiment of a coating chamber for depositing a preferred hard coating. A vacuum deposition chamber 100 is provided to coat the substrate sample. The precursor inlet system 110 includes a metal pipe and a gas distribution ring through which a liquid precursor is injected, preferably a low vapor pressure silicone. The precursor access system 110 is shown to be introduced into the chamber 100 via the side wall of the chamber. An alternative arrangement is to inject the precursor into the chamber 100 through the top of the chamber 1 15 via a gas jet. The sample is loaded into the chamber from the top of the chamber 115 or through a load lock (not shown). The chamber is surrounded by a cylinder with parallel plates 1 1 7 at the top and bottom. An energy supply was used to bias the electrodes (RF-13. 56 MHz). In practice, the system M is pumped down " using a traditional vacuum procedure. Close the gate valve and front vacuum line valve (not shown) and backfill the system with dry nitrogen or argon until the display reaches atmosphere

第10頁 533228 室頂部打開，使用包括夾子任何夾具或固定裝置將欲塗本發明之方法能夠幸昆柱接輥》柱糸統能夠由清和將零件裝入系統基板支架上，以及以轉動，傾斜，或五、發明說明（7) 壓。然後將膠帶等等之電極上。以液體接蒸氣輸送系份。必要時上。將先質控制先質液混合氣體’ 以機械°即以達到高真瓣，如滿輪之其它高真次法少量進基板支架上移除塗佈零對於較大中進行。此開報柱之運人組成。瞭時，欲塗佈理。將基板垂之污染降至蒸氣輸送系統統係一種真空，將先質貯存急驟蒸發為蒸體流過毛細管如氬幫助先質筒將該室形成空。能夠使用分子唧筒，急空唧統。根據行。在此類例，將該室抽氣件（基板）。量而.言輸機構5 解到當在之基板可將先質導入沉技術領域中已在貯器中並輸氣。使用質量之流速。而非蒸發。雛型，繼之以其它唧取系統冷唧筒，或真本發明方法需中，基板係架，進行沉積，直定向較佳，以將微粒或碎最低。以低擾動真空唧取將，螺絲，束緊夾，佈之基板1 5 0置於積室中。該液體接知之傳統現成組送至急驟蒸發器流量控制器精確地必需性，能夠使用底部吹風唧筒唧取，具有或不具凝氣空技術領域中已知要之塗層能夠以批置在沉積室内部之將該室通風’繼之於輥柱接輥柱系統潔模件，捲繞和解中之機械化/機器應加工期間所要求定向，或用手處片凝聚和基板表面沉積室抽氣，以將Page 10 533228 The top of the chamber is opened, and the method to be coated with the present invention can be applied using any fixture or fixing device including a clip. , Or V. Description of the invention (7) Press. Then put tape, etc. on the electrodes. Liquid to vapor delivery system. Go on if necessary. The precursor is controlled by the precursor fluid and the mixed gas ’is mechanically turned to achieve a high true flap, such as a full round of other high true times, and a small amount is inserted into the substrate holder to remove the coating zero. For larger medium. The carrier of this opening column is composed. When it is time, you want to apply it. The contamination of the substrate is reduced to a vapor delivery system, which is a vacuum system. The precursor storage is rapidly evaporated into a stream of vapor through a capillary such as argon to help the precursor cylinder empty the chamber. Able to use molecular tube, emergency air system. Under OK. In this case, the chamber is evacuated by a piece (substrate). In terms of quantity, the transmission mechanism 5 can be used to introduce precursors into the sink in the technical field and transfer the gas. Use mass flow rate. Rather than evaporation. The prototype, followed by other extraction systems, cold heading cylinders, or the actual method of the present invention requires the substrate to be framed and deposited. The straight orientation is better to minimize particles or debris. Use a low-perturbation vacuum to pick up, place the screws, tightening clamps, and cloth substrate 150 in the chamber. The liquid ready-made traditional ready-made group is sent to the flash evaporator. The flow controller is precisely necessary. It can be picked up by using a bottom blower drum. The coating with or without the condensed air technology can be placed in the deposition chamber in batches. The interior of the chamber is ventilated ', followed by the roll-to-roller system cleaning module, the mechanization in the winding and dismantling / machine should be oriented during processing, or the sheet condensate by hand and the substrate surface deposition chamber is evacuated to will

第11頁 533228 五、發明說明（8) 沉積於基板表面上之微粒和碎片抽氣。在裝基板後將室抽氣之基礎壓力低於1 0至2 0毫托耳。沉積期間室壓係介於5 0至5 0 0毫托耳之間。將先質和另外的氣體，如氬，氫和/或氧導入以提高室壓。能夠使用節流閥調整室壓。塗佈前將基板在沉積室内部離子清潔。 ' 基板等離子體清潔能夠以許多氣體進行，如氬，氧和氫。等離子體清潔期間氣體之選擇係取決於基板形式。基 _ 板等離子體清潔係以RF輝光放電進行。導入清潔氣體直到室壓在5 0至5 0 0毫托耳範圍内。以R F電位將電極加能激發輝光放電。放電期間，能夠使用約0 . 0 0 5至約5 . 0 kV之基 0 板偏壓。固定RF之頻率。然而，能夠亦使用其它頻率（1 0 0 Κ Η z至1 Ο Ο Μ Η z )。亦能夠使用其它沉積塗層領域中已知之離子來源產生離子，如卡夫曼（Kaufmann)型離子來源，RF 線圈，ECR來源等等。頃發現等離子體清潔法有效地移除烴污染，和其它污染物，以及改良基板上所沉積塗層之黏附。將近基板清潔終了，將蒸氣化之有機矽先質，較佳為包含C，Η，S 1和0之矽氧烷導入室中。該先質能夠使用液體接蒸氣輸送系統導入系統中，該系統係由該領域中已知之流量控制器，加熱器，分配器組成。該先質較佳具有1至 1 0個矽原子。較佳先質為HMD SO且係使用如氬之載體氣體運輸至該室。將如氫和氧之額外氣體與該先質一起導入。^ 其它如甲烷，乙烯，丁烷，CF4，C2F6之氣體能夠用以改變 -薄膜性質。該RF等離子體放電引起先質碎斷。Page 11 533228 5. Description of the invention (8) The particles and debris deposited on the substrate surface are evacuated. The base pressure for evacuating the chamber after mounting the substrate is below 10 to 20 millitorr. Ventricular pressure during deposition is between 50 and 500 mTorr. A precursor and another gas such as argon, hydrogen, and / or oxygen are introduced to increase the chamber pressure. Room pressure can be adjusted using a throttle valve. The substrate is ion-cleaned inside the deposition chamber before coating. '' Substrate plasma cleaning can be performed with many gases such as argon, oxygen, and hydrogen. The choice of gas during plasma cleaning depends on the substrate form. The substrate plasma cleaning is performed by RF glow discharge. Introduce clean gas until the chamber pressure is in the range of 50 to 500 mTorr. Energizing the electrode at the R F potential excites a glow discharge. During the discharge, a base plate bias of about 0.05 to about 5.0 kV can be used. Fixed RF frequency. However, other frequencies (100 k Η z to 100 Μ Η z) can also be used. Ions can also be generated using other ion sources known in the field of deposited coatings, such as Kaufmann-type ion sources, RF coils, ECR sources, and so on. It was found that the plasma cleaning method effectively removes hydrocarbon contamination and other contaminants, and improves the adhesion of the coating deposited on the substrate. Near the end of the substrate cleaning, the vaporized organosilicon precursor, preferably a siloxane containing C, plutonium, S 1 and 0, is introduced into the chamber. The precursor can be introduced into the system using a liquid-to-vapor delivery system, which is composed of flow controllers, heaters, and distributors known in the art. The precursor preferably has 1 to 10 silicon atoms. The preferred precursor is HMD SO and is transported to the chamber using a carrier gas such as argon. Additional gases such as hydrogen and oxygen are introduced with the precursor. ^ Other gases such as methane, ethylene, butane, CF4, C2F6 can be used to change the film properties. This RF plasma discharge causes fragmentation of the precursor.

第12頁 533228 五、發明說明（9) 上述沉積法之變化包括：（a)使用濺射矽和氧氣作為S 1 和0之來源；（b )使用固體S i 02作為S i和0之來源；（c )使用S 1 H4和含氧氣體作為S i之來源；（d )使用石墨靶，氫，和氫氣作為C和Η之來源。可以使用上述方法之組合。該塗層沉積較佳係以 R F電容偶合放電（C C D )維持。能夠使用單一極板組態。基板係接合於極板。然後施加 RF或PDC電壓。以電容RF放電而論，RF之頻率係在100 kHz至100 MHz之間。在另一方法中，能夠將大型RF天線置於該室内部以激發放電。天線能夠以銅，不鏽鋼，或其它技藝材料已知之狀態製造。能夠在天線表面應用保護塗層，如高嶺土，以避免濺射。通常在沉積法期間於基板施加R F電壓。該R F電壓有助於將沉積之塗層密集化與硬化。R F電壓範圍為約0 . 0 0 5至5 KV，能夠改變以適合塗層性質。未使用外部基板加熱。由於離子撞擊產生熱，此引起基板加熱達到7 0 t。必要時，能夠使用封閉電流熱交換器將基板支架活動性冷卻。適合塗層性質之能力與在低於7 0 °C沉積這些塗層之能力，使得能夠適合塗佈各種彈性基板材料，如聚碳酸酯， PET， PE， Kapton ， Mylar， U Item 和 Tori on 〇咸相信此’’可調和力n和缺乏熱失配問題歸因於塗層之優良黏附和低應力。除了優良黏附外，本發明之塗層具有高硬度，可見和紅外波長内之優良透明度，低薄膜應力，非常高電阻，高度彈性，UV抗力，良好抗化學性，高度環境安定性，低表面Page 12 533228 V. Description of the invention (9) The changes of the above deposition method include: (a) using sputtered silicon and oxygen as the source of S 1 and 0; (b) using solid S i 02 as the source of S i and 0 (C) using S1H4 and an oxygen-containing gas as the source of Si; (d) using a graphite target, hydrogen, and hydrogen as the sources of C and krypton. A combination of the above methods can be used. The coating deposition is preferably maintained by an R F capacitor coupling discharge (C C D). Ability to use a single plate configuration. The substrate is bonded to the electrode plate. Then apply RF or PDC voltage. In terms of capacitor RF discharge, the frequency of RF is between 100 kHz and 100 MHz. In another method, a large RF antenna can be placed inside the room to excite a discharge. The antenna can be manufactured in a state known from copper, stainless steel, or other technical materials. A protective coating, such as kaolin, can be applied to the antenna surface to avoid sputtering. The RF voltage is usually applied to the substrate during the deposition method. This RF voltage helps to dense and harden the deposited coating. The R F voltage ranges from about 0.05 to 5 KV and can be changed to suit the properties of the coating. No external substrate heating is used. Due to the heat generated by the ion impact, this causes the substrate to heat up to 70 t. If necessary, the substrate holder can be movably cooled using a closed-current heat exchanger. The ability to adapt to the properties of the coating and the ability to deposit these coatings below 70 ° C make it suitable for coating a variety of flexible substrate materials such as polycarbonate, PET, PE, Kapton, Mylar, U Item and Tori on. Xian believes that this `` tunable force n and lack of thermal mismatch problems is due to the coating's excellent adhesion and low stress. In addition to excellent adhesion, the coating of the present invention has high hardness, excellent transparency in visible and infrared wavelengths, low film stress, very high resistance, high elasticity, UV resistance, good chemical resistance, high environmental stability, and low surface.

第13頁 533228 五、發明說明（ίο) 能和高水接觸角。該塗層具有高硬度和使用微壓痕計II s測量微壓痕之彈性模數。因為高硬度，該塗層具有良好抗碎性和耐久性。該塗層呈現硬度在2至10 GPa之間（典型上在5至7.5 GPa之間）。為了對照，軟鋼之硬度為約3至4 GPa，玻璃則為約6 至8 G P a (圖2 )。因此典型硬質塗層較軟鋼硬且如玻璃般硬。硬質塗層之典型彈性模數係在30至50 GPa之間。塗層抗磨性係使用鋼絨在塗佈聚碳酸酯基板上磨擦6至8次而測試。通過鋼絨磨擦之塗層為測試成功。該塗層之光學性質並未一致且無來自鋼絨對於塗層之物理傷害。該塗層在可見波長具有優良透射。該塗層在波長範圍 3 6 0至9 0 0毫微米之間透射超過8 5%。該塗層在波長範圍4 0 0 至9 0 0毫微米之間透射超過9 0 % (圖3 )。且該塗層在紅外範圍内透射非常高。塗層之折射率能夠適合於在5 4 0毫微米為 1 . 6 至 2. 5。該塗層呈現非常低薄膜應力。塗層内殘餘應力頃使用該技藝中已知之史東尼（Stoney)方程式以鐳射電子束反射技術特徵化。殘餘應力具壓縮力且在9 0至4 0 0 MPa範圍内。薄膜内低應力之原因為低溫沉積法和獨特之薄膜結構。該塗層電阻在室溫超過1 0 e + 1 3至1 0 e + 1 4。該塗層亦具有非常高介電強度和低漏電密度。塗層之介電強度大於1 ΜV/公分，介電常數為約3. 5至5. 0。塗層之彈性頃以測量塗佈聚酿亞胺（K a p t ο η®和M y 1 a r® ) 基板能夠彎曲而不斷裂或塗層去層壓之最低彎曲半徑而量Page 13 533228 V. Description of the invention (ίο) Can contact high water. This coating has high hardness and uses the microindenter II s to measure the elastic modulus of the microindentation. Because of its high hardness, the coating has good chip resistance and durability. The coating exhibits a hardness between 2 and 10 GPa (typically between 5 and 7.5 GPa). For comparison, the hardness of mild steel is about 3 to 4 GPa, and that of glass is about 6 to 8 G Pa (Figure 2). So typical hard coatings are harder than soft steel and as hard as glass. Typical elastic modulus of hard coatings is between 30 and 50 GPa. Coating Abrasion resistance was tested by rubbing steel wool on a coated polycarbonate substrate 6 to 8 times. The coating that passed the steel wool abrasion was successful. The coating's optical properties are not consistent and there is no physical damage to the coating from steel wool. The coating has excellent transmission at visible wavelengths. The coating transmits more than 85% in the wavelength range 360 to 900 nm. The coating transmits more than 90% in the wavelength range of 400 to 900 nanometers (Figure 3). And the coating has very high transmission in the infrared range. The refractive index of the coating can be adapted from 1.6 to 2.5 at 540 nm. The coating exhibits very low film stress. Residual stresses in the coating are characterized by laser electron beam reflection using the Stoney equation known in the art. The residual stress is compressive and is in the range of 90 to 400 MPa. The reason for the low stress in the thin film is the low temperature deposition method and the unique thin film structure. The coating resistance exceeds 10 e + 1 3 to 10 e + 1 4 at room temperature. The coating also has very high dielectric strength and low leakage density. The dielectric strength of the coating is greater than 1 MV / cm, and the dielectric constant is about 3.5 to 5.0. The elasticity of the coating is measured by the minimum bending radius of the coated polyimide (K a p t ο η® and My 1 a r®) substrate which can be bent without breaking or the coating is delaminated.

第14頁 533228 五、發明說明（11) 化。該塗層抗斷裂，至彎曲半徑為7 / 3 2"塗層彈性超越平面顯示器應用所需。塗層於凸出彎曲模式較相反之凹入彎曲模式具彈性，因為薄膜内之壓縮應力。塗層延長暴露於照光之抗劣化頃經調查。將塗層接受鎢絲燈照光（相當於 0 . 5陽光）1 5 0 0小時。該塗層顯示於光學和物理性質無改變，其表示塗層相當安定。對於所有與FPD成形加工相關之化學品具良好抗性係塑膠硬質塗料之基本性質。該塗層頃經根據ASTM D 1 3 0 8測量對於甲醇，丙酮，I P A，3 0 %過氧化氫，和3 0 %氫氧化銨之抗性。在所有例中，塗層顯示無褪色，起水泡，黏性喪失，或光學特徵改變。該塗層頃經在酸和鹼環境中測試腐 I虫抗性和化學惰性。該塗層不受如H C 1，H F和Η N 0 3之酸，與如ΚΟΗ之驗影響。為了承文F P D成形加工需要之南溫’基本上該硬質塗層，以及基板，能夠承受2 0 (TC至少1小時而其物理或光學性質無劣化。在這些塗層上進行之熱安定性研究提出它們能夠在氧化環境中克服達4 0 0 °C之溫度2小時。此遠高於 F P D應用之必要條件。塑膠顯示器之另一必要條件為避免濕氣之阻擋保護。該塗層必需對於濕氣和腐蝕氣體不可滲透，所以避免滲透下面的塑膠基板，因而保護產品内部電路。塗層係作為對於氧和水蒸氣之優良阻擋。塗層顯示氧傳導速率降低為未塗佈聚合物基板之1 . 9至8 0. 2倍。塗層顯示水蒸氣傳導速率降低為未塗佈聚合物基板之1. 4至1 2. 1倍。有效阻擔保護Page 14 533228 V. Description of the invention (11). The coating is resistant to fracture to a bending radius of 7/3 2 " The coating is more flexible than flat panel display applications. The coating is more elastic in convex bending mode than in concave bending mode due to compressive stress in the film. The resistance of the coating to prolonged exposure to light has been investigated. The coating was exposed to tungsten light (equivalent to 0.5 sunlight) for 15 hours. The coating shows no change in optical and physical properties, which indicates that the coating is quite stable. Good resistance to all chemicals related to FPD forming is a basic property of plastic hard coatings. The coating was tested for resistance to methanol, acetone, IPA, 30% hydrogen peroxide, and 30% ammonium hydroxide in accordance with ASTM D 1 308. In all cases, the coating showed no discoloration, blisters, loss of viscosity, or changes in optical characteristics. The coating was tested for rot resistance and chemical inertness in acid and alkaline environments. The coating is not affected by acids such as H C 1, H F and Η N 0 3, and by tests such as KΚ. In order to support the FPD molding process, Nanwen's basically the hard coating, and the substrate, can withstand 20 (TC for at least 1 hour without degradation of its physical or optical properties. Thermal stability studies performed on these coatings It is proposed that they can overcome temperatures of up to 400 ° C for 2 hours in an oxidizing environment. This is far higher than the necessary condition for FPD applications. Another necessary condition for plastic displays is to avoid the barrier protection of moisture. The coating must be resistant to humidity Gases and corrosive gases are impermeable, so avoid the penetration of the plastic substrate below, thus protecting the internal circuit of the product. The coating is an excellent barrier against oxygen and water vapor. The coating shows that the oxygen transmission rate is reduced to one of the uncoated polymer substrate 9 to 8 0.2 times. The coating shows a reduction in water vapor transmission rate from 1.4 to 12. 1 times the uncoated polymer substrate. Effective resistance to protection

第15頁 533228 五、發明說明（12) 係視聚合物基板之選擇而定。阻擋塗層之重要觀點之一係其對水之親和力。本塗層為高度疏水性（避免水由於低表面能而滲開），並呈現高水接觸角。接觸角越高（表面能越低），塗佈表面被水潤濕越低。該塗層之表面能為2 7至3 8達因/公分，水接觸角為7 0 * 至92。薄膜厚度能夠介於5 Ο A至1 0微米之間。以下實例僅說明本發明之觀點，不應該被認定為限制本發明。實例1 1 將聚乙烯和氟聚合物之4 X 4平方英吋清潔基板架置於底部電極上。將於清潔劑中清潔，繼之以異丙醇清潔，然後以氮氣吹乾之矽，玻璃，碳鋼，和不鏽鋼基板之控制樣品易架置於基板支架上。將該室抽氣至最終壓力為2 5毫托耳。將氬導入該室中以將壓力提高至1 8 0毫托耳。使用 3 0 0 W之RF基板能量以將基板偏壓以便就地等離子體清潔。將基板等離子體清潔5分鐘。清潔後基板能量傾斜至 5 0 0 W，其相當於150V之基板偏壓。然後經由液體蒸氣輸送系統導入先質。於此沉積中使用先質六氫二矽氧烷 (HMDSO)。使用0. 06克/分鐘之先質流速。同時導入額外加Μ 工氣體，如氫和氧。氫流速為3 0 s c c m，氧流速為3 3 . 5 seem。沉積係在以上環境下進行4 5分鐘。沉積後基板支架溫度為約5 5 °C 。此產生厚度0 . 8 5微米，高度黏性之塗層。該塗層呈現硬度為7 G P a ’在碳鋼基板上使用微壓痕計Page 15 533228 V. Description of the invention (12) It depends on the choice of polymer substrate. One of the important points of barrier coatings is their affinity for water. This coating is highly hydrophobic (avoids water seepage due to low surface energy) and exhibits high water contact angles. The higher the contact angle (the lower the surface energy), the less the coated surface is wetted with water. The surface energy of the coating is 27 to 38 dyne / cm, and the water contact angle is 70 * to 92. The film thickness can be between 50 μA and 10 μm. The following examples merely illustrate the point of view of the invention and should not be considered as limiting the invention. Example 11 1 A 4 x 4 square inch clean substrate holder of polyethylene and fluoropolymer was placed on the bottom electrode. The control samples of silicon, glass, carbon steel, and stainless steel substrates are cleaned in a detergent, followed by isopropyl alcohol, and then dried with nitrogen. The control samples are easy to place on the substrate holder. The chamber was evacuated to a final pressure of 25 millitorr. Argon was introduced into the chamber to increase the pressure to 180 millitorr. An RF substrate energy of 300 W was used to bias the substrate for in-situ plasma cleaning. The substrate was plasma cleaned for 5 minutes. After cleaning, the substrate energy is tilted to 500 W, which is equivalent to a substrate bias of 150V. The precursor is then introduced via a liquid vapor delivery system. The precursor hexahydrodisilazane (HMDSO) was used in this deposition. A precursor flow rate of 0.06 g / min was used. At the same time additional processing gases such as hydrogen and oxygen are introduced. The hydrogen flow rate is 30 s c cm and the oxygen flow rate is 3 3.5 seem. Deposition takes place in the above environment for 4 5 minutes. The substrate holder temperature after deposition is about 5 5 ° C. This results in a highly adhesive coating with a thickness of 0.85 microns. The coating exhibits a hardness of 7 G P a ’using a micro-indenter on a carbon steel substrate

第16頁 533228 五、發明說明（13) I I s測量微壓痕之彈性模數為6 2 G P a。塗層為透明且在 5 4 0毫微米之透射為9 1 . 6 %。該塗層呈現在5 4 0毫微米之波長折射率為1 . 8 6。實例2 以史考特膠帶黏性測試（Scotch Tape Adhesion Test) 測試來自實例1之塗佈基板黏性。測試之基板為氟聚合物，聚碳酸酯，玻璃，碎和碳鋼基板。在所有基板上黏性良好且未觀察到塗層去層壓或去黏附。實例3 將聚乙烯，環系聚烯和和氟聚合物之4 X 4平方英吋清潔基板架置於底部電極上。將於清潔劑中清潔，繼之以異丙醇清潔，然後以氮氣吹乾之矽，玻璃，碳鋼，和不鏽鋼基板之控制樣品易架置於基板支架上。將該室抽氣至最終壓力為25毫托耳。將氬導入該室中以將壓力提高至180毫托耳。使用3 0 0 W之RF基板能量以將基板偏壓以變就地等離子體清潔。將基板等離子體清潔5分鐘。清潔後基板能量傾斜至5 3 8 W，其相當於1 6 2 V之基板偏壓。然後經由液體蒸氣輸送系統導入先質。於此沉積中使用先質HMDS0。使用 0. 0 6克/分鐘之先質流速。同時導入額外加工氣體，如氫和氧。氫流速為3 0 s c c m，氧流速為4 5 · 6 s c c m。沉積係在以上環境下進行3 8分鐘。沉積後基板支架溫度為約5 0 °C。此產生厚度0. 7 3微米，高度黏性之塗層。該塗層在碳鋼基板上使用微壓痕計I I s測量微壓痕呈現硬度為6. 2 GPa。塗層為透明且在4 0 0毫微米之透射為8 1 . 2 %。該塗層呈現在Page 16 533228 V. Description of the invention (13) The elastic modulus of microindentation measured by I I s is 6 2 G P a. The coating was transparent and had a transmission of 51.6 nm at 9 1.6%. The coating exhibited a refractive index of 1.86 at a wavelength of 540 nm. Example 2 The coated substrate from Example 1 was tested by the Scotch Tape Adhesion Test. The substrates tested were fluoropolymer, polycarbonate, glass, broken and carbon steel substrates. Good adhesion on all substrates and no coating delamination or de-adhesion was observed. Example 3 A 4 x 4 square inch clean substrate holder of polyethylene, cyclopolyene, and fluoropolymer was placed on the bottom electrode. The control samples in silicon, glass, carbon steel, and stainless steel substrates are cleaned in a cleaning agent, followed by isopropyl alcohol, and then dried with nitrogen, and are easily placed on a substrate holder. The chamber was evacuated to a final pressure of 25 mTorr. Argon was introduced into the chamber to increase the pressure to 180 mTorr. An RF substrate energy of 300 W was used to bias the substrate for in-situ plasma cleaning. The substrate was plasma cleaned for 5 minutes. After cleaning, the substrate energy tilts to 5 3 8 W, which is equivalent to a substrate bias of 16 2 V. The precursor is then introduced via a liquid vapor delivery system. The precursor HMDSO was used in this deposition. A precursor flow rate of 0.06 g / min was used. At the same time additional process gases such as hydrogen and oxygen are introduced. The hydrogen flow rate is 30 s c c m and the oxygen flow rate is 4 5 · 6 s c c m. Deposition takes place in the above environment for 38 minutes. The substrate holder temperature after deposition was about 50 ° C. This results in a thickness of 0.73 microns, a highly viscous coating. 2 GPa。 The coating on a carbon steel substrate using a micro-indenter I I s measurement micro-indentation showed a hardness of 6.2 GPa. The coating was transparent and had a transmission of 400. 2% at 81.2%. The coating appears on

第17頁 533228 五、發明說明（14) 5 4 〇毫微米之透射為9 0 . 3 %。該塗層在波長5 4 0毫微米之折射率為1 · 7 6。以Μ 0 C Ο N (明尼波里司（M i η n e a p〇1 i s )，Μ N ) 測試，使用A S T Μ，D I N和J I S方法測量在氟聚合物和聚乙烯上之塗層之阻擋性質。氧透射率從未塗佈基板之1. 9倍降低至8 0. 2倍。水蒸氣透射率從未塗佈基板之1. 4倍降低至1 2 . 1倍。實例4 將清潔之4英吋長l/4n OD Tygon®切管架置於底部電極上。將切管架置於二個末端柱上，所以該管長度被架高且不語以部電極接觸。將於清潔劑中清潔，繼之以異丙醇清潔，然後以氮氣吹乾之矽，玻璃，碳鋼，和不鏽鋼基板之控制樣品易架置於基板支架上。將該室抽氣至最終壓力為 2 5毫托耳。將氬導入該室中以將壓力提高至1 8 0毫托耳。使用3 0 0 W之RF基板能量以將基板偏壓以便就地等離子體清潔。將基板等離子體清潔5分鐘。清潔後基板能量傾斜至 5 3 8 W，其相當於1 6 2 V之基板偏壓。然後經由液體蒸氣輸送系統導入先質。於此沉積中使用先質Η M D S 0。使用0. 0 6克/ 分鐘之先質流速。同時導入額外加工氣體，如氫和氧。氫流速為3 0 s c c m，氧流速為4 5 . 6 s c c m。沉積係在以上環境下進行3 8分鐘。沉積後基板支架溫度為約5 0 °C。此產生厚度0. 7 3微米，高度黏性之塗層。該塗層在碳鋼基板上使用微壓痕計I I s測量微壓痕呈現硬度為6. 2 GPa。塗層為透明且在4 0 0毫微米之透射為8 1 . 2 %。該塗層呈現在5 4 0毫微米之透射為90. 3%。該塗層在1 0 2 0 cur1波長附近呈現強Si-0Page 17 533228 V. Description of the invention (14) The transmission of 540 nm is 90.3%. The coating has a refractive index of 1.76 at a wavelength of 540 nm. The barrier properties of coatings on fluoropolymers and polyethylene were measured using M 0 C 0 N (Minneapolis, M N) test using AST M, DIN and JIS methods. . The oxygen transmittance was reduced from 1.9 times of the uncoated substrate to 8 0.2 times. The water vapor transmission rate was reduced from 1.4 times to 12 times that of the uncoated substrate. Example 4 A clean 4-inch long l / 4n OD Tygon® tube holder was placed on the bottom electrode. Place the tube holder on the two end posts, so the tube is raised in length and does not touch the electrodes. The control samples in silicon, glass, carbon steel, and stainless steel substrates are cleaned in a cleaning agent, followed by isopropyl alcohol, and then dried with nitrogen. The control samples are easily placed on the substrate holder. The chamber was evacuated to a final pressure of 25 millitorr. Argon was introduced into the chamber to increase the pressure to 180 millitorr. An RF substrate energy of 300 W was used to bias the substrate for in-situ plasma cleaning. The substrate was plasma cleaned for 5 minutes. After cleaning, the substrate energy is tilted to 5 3 8 W, which is equivalent to a substrate bias of 16 2 V. The precursor is then introduced via a liquid vapor delivery system. The precursor Η M D S 0 was used in this deposition. A precursor flow rate of 0.06 g / min was used. At the same time additional processing gases such as hydrogen and oxygen are introduced. The hydrogen flow rate was 30 s c cm, and the oxygen flow rate was 45.6 s c cm. Deposition takes place in the above environment for 38 minutes. The substrate holder temperature after deposition was about 50 ° C. This produces a highly viscous coating with a thickness of 0.73 microns. 2 GPa。 The coating on a carbon steel substrate using a micro-indenter I I s measurement micro-indentation showed a hardness of 6.2 GPa. The coating was transparent and had a transmission of 400% at 400 nm. 3%。 The coating exhibited a transmission of 50.4 nm is 90.3%. The coating exhibits strong Si-0 near the wavelength of 1 0 2 0 cur1

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Claims

5p322^ 公告5p322 ^ announcement

號 88112697 9L ζ·： β- 修正六-中專彳1JnzH 1 . 一種用於塑膠基板之硬質塗層，其包括非晶形結構之碳，氫，矽和氧，其中該塗層係在7 0 °C或低於該溫度及5 0 至500毫托耳之壓力下沈積，且該塗層具有微壓痕硬度介於2至10 GPa間之性質。 2 .根據申請專利範圍第1項之塗層，其包括一種玻璃狀 S i - 0網路。 3. 根據申請專利範圍第1項之塗層，其包括一種包含 Si-0，C-H，Si-H和Si-C之多組份結構。 4. 根據申請專利範圍第3項之塗層，其中主要為Si-0和 C-Η ° 5. 根據申該塗層之2 5 6. 根據申塗層之2 5原至少該塗層矽含量為該比，且氧含子百分比。 7. 根據申 1 . 7克/cc至 8. 根據申 RF放電等離 9 .根據申密度，低溫請專利範圍第1項之塗層，其中該碳含量大於原子百分比。請專利範圍第1項之塗層，其中該碳含量為該子百分比至該塗層之6 5原子百分比，氫含量為之1原子百分比上至該塗層之4 0原子百分比，塗層之1 0原子百分比上至該塗層之3 0原子百分量為該塗層之8原子百分比上至該塗層之40原請專利範圍第1項之塗層，其中塗層之密度在 2 · 0克/ c c之間變化。請專利範圍第1項之塗層，其中該塗層係經由子體法合成。請專利範圍第1項之塗層，其中該塗層係以低等離子體強化化學蒸氣沉積法沉積。No. 88112697 9L ζ ·: β-corrected six-secondary school 1JnzH 1. A hard coating for plastic substrates, which includes amorphous carbon, hydrogen, silicon and oxygen, where the coating is at 70 ° C or below this temperature and a pressure of 50 to 500 millitorr, and the coating has a micro-indentation hardness between 2 and 10 GPa. 2. The coating according to item 1 of the patent application scope, which comprises a glassy Si-0 network. 3. The coating according to item 1 of the patent application scope, which includes a multi-component structure comprising Si-0, C-H, Si-H and Si-C. 4. The coating according to item 3 of the scope of patent application, which is mainly Si-0 and C-Η ° 5. According to the application of 2 5 6. According to the application of 2 5 the original silicon content of the coating is at least Is the ratio, and the percentage of oxygen contains. 7. According to Shen 1.7 g / cc to 8. According to Shen RF discharge plasma 9. According to Shen density, low temperature Please apply for coating of item 1 of patent scope, where the carbon content is greater than atomic percentage. Please apply for the coating of item 1 of the patent scope, wherein the carbon content is from the sub-percentage to 65 atomic percent of the coating, the hydrogen content is from 1 atomic percent to 40 atomic percent of the coating, 0 atomic percent up to 30 atomic percent of the coating is 8 atomic percent of the coating up to 40 percent of the coating of the original patented item 1 of the coating, wherein the density of the coating is 2.0 grams / cc. The coating according to item 1 of the patent scope, wherein the coating is synthesized by the daughter method. The coating according to item 1 of the patent, wherein the coating is deposited by a low plasma enhanced chemical vapor deposition method.

O:\59\59640-910828.ptc 第21頁 533228 案號 88112697 月曰修正六、申請專利範圍 1 0 .根據申請專利範壓痕硬度介於5至7. 5 1 1 .根據申請專利範至9 0 0毫微米間之波長 1 2 .根據申請專利範至9 0 0毫微米間之波長 1 3 .根據申請專利範能為27至38達因/公分 1 4 .根據申請專利範觸角為70至90。 1 5 .根據申請專利範厚度為5 0埃至1 0微米< 1 6 .根據申請專利範性。 1 7 .根據申請專利範滲透。圍第1項之塗層，其中該塗層具有微 GPa間之性質。圍第1項之塗層，其中該塗層在360 具大於85%之UV透射。圍第1項之塗層，其中該塗層在400 具大於90 %之UV透射。圍第1項之塗層，其中該塗層之表面〇圍第1項之塗層，其中該塗層之水接圍第1項之塗層，其中該塗層之薄膜 ) 圍第1項之塗層，其中該塗層為疏水圍第1項之塗層，其中該塗層為不可O: \ 59 \ 59640-910828.ptc Page 21 533228 Case No. 88112697 Amendment VI. Patent application scope 1 0. According to the patent application, the indentation hardness is between 5 and 7. 5 1 1. According to the patent application Wavelength between 900 nm 1 2. Wavelength between 900 nm from patent application 1 3. Energy range from 27 to 38 dyne / cm 1 according to patent application range. Antenna 70 from patent application range To 90. 15. According to the patent application, the thickness is 50 angstroms to 10 micrometers < 16. According to the patent application. 1 7. Penetration according to patent application. The coating according to item 1, wherein the coating has a property of micro GPa. The coating of item 1 wherein the coating has a UV transmission of greater than 85% at 360. The coating of item 1 wherein the coating has a UV transmission of more than 90% at 400. The coating of item 1 wherein the surface of the coating is the coating of item 1 where the water of the coating meets the coating of item 1 where the film of the coating) of item 1 Coating, wherein the coating is a coating of hydrophobic item 1, wherein the coating is not

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