TW420723B - Method of forming diamond like carbon film(DLC), DLC film formed thereby, use of the same, field emitter array and field emitter cathodes - Google Patents

Abstract

The present invention relates to a method for forming substantially hydrogen free DLC layers, wherein DLC layer of thickness about 1 to 100 nanometers is deposited over a sample substrate or a field emitter array and subsequently exposed to etching plasma comprising fluorine gas, wherein during the latter step, hydrogen contained in the substrate is eliminated by chemical etching reaction with fluorine, wherein steps to form the hydrogen free DLC layer can be repeated to obtain a predetermined thickness of a DLC film.

Description

^20723 修正 θ 1·~~~—86i〇RnfiA 五、發明說明(1) .技術範園 本發明係有關於一 氣相沈積法）方& E C V 〇 (電漿輔助化學 上無氫的(類鑽碳）"別是大體 膜。本發明亦係有關於利用此方法形成之DL c 場效發射陰極，並作為場效發射顯示器之 與含有…膜之膜之場效發射器陣列 先前技術： 一气言之’不含氫的DLC歲：a：人# t 於其S P3部分 ， 、，、含虱的相較之下，由‘ S V e e…：所：相當值得注意，例如見之V · veerasamy先生 v E 1 6 C 3 7 5 3 1 9 ( 1 9 〇 . ' d ' S 1 3 1 e c k e n z i e 先生的 T h i n 9 Ί D · R · M — 2 1 2，2 3 2 ( 9 9 2 )。而 W 1 d F H m s D L C膜，在作為真空微電子袈有負電子親和性的 ，具有很大的潛力，因此，已經射器運用方面 M.W.Ge “先生的ΙΕΕΠ5的研究，譬如： 12.456(1991) 'N.c.i “"·^ 20723 Correction θ 1 · ~~~ —86i〇RnfiA V. Description of the Invention (1). Technical Field The present invention relates to a vapor deposition method) & ECV 〇 (plasma-assisted chemically hydrogen-free (class (Drilling carbon) " Other than a bulk film. The present invention also relates to the field-effect emitter array of the DL c field-effect cathode formed by this method, and the field-effect emitter array of the field-effect display and the film containing ... In one word, the age of DLC without hydrogen: a: man # t compared to its SP3 part,…, compared with lice, from ‘SV ee…: So: quite noteworthy, see for example V Mr. Veerasamy v E 1 6 C 3 7 5 3 1 9 (1 9 〇. 'd' S 1 3 1 Mr. Eckenzie's T hin 9 Ί D · R · M — 2 1 2, 2 3 2 (9 9 2) The W 1 d FH ms DLC film has a great potential for negative electron affinity as a vacuum microelectron. Therefore, it has been studied in the application of emitters by MWGe "Mr. IEEΠ5, such as: 12.456 (1991 ) 'Nci "" ·

Electron-Lett.,9q u先生的 1 9 9 3 ) 。D L C作為發射材1 5 9 6 ( 特發射特性一低場效冷發射與發點’在於它的獨 的極佳熱導性可以預期從DL C瞪二^生。此外，DL c 的電流。可以從上述參考資料得β的發射器獲得很高 場效發射顥示器的場效發射器材料L C膜典型地係作為 ---------- ° ~般說來場效發射 $ 5頁 射陰極與 在實作裡 ，來自冷 其方式一 最常採用 。然而使 ，與D L 激勵電壓 爾（T 〇 D L C的 為極佳的 鋇或鎢錳 被廣泛地 >4 射陣列所 用P E C ，典塑地 先生的T (19 9 膜硬度的 或是離子 r g先生 3(19 派沈積的 e n z iElectron-Lett., Mr. 9q u 1 9 9 3). DLC as the emitting material 1 5 9 6 (special emission characteristics-low field-effect cold emission and emission point 'lies in its unique excellent thermal conductivity can be expected from DL C stark. In addition, DL c current. Can The β-emitter obtained from the above reference material has a very high field-effect launch. The LC film of the field-effect launcher material is typically used as a field-effect launch. $ 5 The sheet-emission cathode is the most commonly used method in practice. However, it is widely used with the DL excitation voltage (T o DLC is excellent barium or tungsten-manganese PEC). Mr. Dian Sui's T (19 9 film hardness or ion Mr. rg 3 (19 pie deposited enzi

玻璃面板構成， ，面板保持报高 陰極陣列的電子 如傳統的電視影 的材料是鑽石、 用金屬或矽作為 C或鑽石相較， 高。另外電子與 r r )以下高真 化學惰性、硬度 場效發射顯示器 尖錐上沈積鑽石 討論。電子發射 1 V /cm，此一強度 420723 案號 五、發明說明（2) 顯示器是由發 物上塗有磷。 被引導而來時 素製造亮光， 射顯示器尖錐 諸如鋇的金屬 些問題，例如 工作功能而致 保持1 0_7陶 題和困難度。 函數，使其成 由在矽、 電子發射器亦 降至少於3 X 屬尖錐場效發 之前，利 較高的氫含量 p e n e e r 2 17*56 部分，而導致 真空電弧沈積 i s e n b e 4 2，2 9 5 用過濾真空電 %，見 M c k 需的電場強度1 V D方法沈積出 高於2 〇 %，見 h i n Sol 2 )。衲入的氫 降低。無氫的D 束沈積得到，見 的 A p p 1 · 7 1) * M c k 無氫D L c ，s e先生的p h y 在透明的傳導氧化 的正電壓。當色素 會轟擊對應的磷元 像管。目前場效發 類鑽碳膜、矽晶及 尖錐材料時具有一 耐久性低，且因高 粒子的擴散，導致 空及尖錐氧化的問 ’特別是它的低功 電子發射材料。 膜所得到的冷陰極 所需的電場強度被 大體上小於傳統金 x 1 〇6 v/cra。 來的DLC臈具有 A D e k e m - "Films 減少了膜内的s p3 L C可以利用過濾 (例如）S · a — P h y s * e n z i e先生利 P3部分高過8 5 s . R v e · l —The glass panel is composed of high-cathode array electrons, such as traditional television films. The material is diamond, and metal or silicon is used as C or diamond. In addition, electrons and r r) are highly chemically inert and hard. Field-emission displays. Diamonds are deposited on the cone. The electron emission is 1 V / cm. This intensity is 420723. Case No. 5. Description of the invention (2) The display is coated with phosphorous. When led, the element produces bright light, shoots the tip of the display, and metal such as barium. Some problems, such as working functions, keep the 10-7 problem and difficulty. Function, it is caused by the high hydrogen content peneer 2 17 * 56 part before the silicon and electron emitters are reduced to less than 3 X belongs to the cone field effect, which leads to vacuum arc deposition isenbe 4 2, 2 9 5 Use filtration vacuum electricity%, see the electric field strength required by Mck 1 VD method deposits more than 20%, see hin Sol 2). The influx of hydrogen decreases. D-beam deposition without hydrogen, see A p p 1 · 7 1) * M c k hydrogen-free D L c, p h y of Mr s e in a transparent conductive oxidation positive voltage. When the pigment will bombard the corresponding phosphor image tube. At present, field-effect diamond-like carbon films, silicon crystals, and pyramid materials have low durability, and due to the diffusion of high particles, the problem of hollow and pyramid oxidation is particularly problematic with its low-power electron-emitting materials. The required electric field strength of the cold cathode obtained by the membrane is substantially smaller than that of conventional gold x 106 v / cra. Coming DLC 臈 has A D e k e m-" Films reduces the s p3 in the membrane L C can be filtered (for example) S · a — P h y s * e n z i e Mr. Lee P3 part is higher than 8 5 s. R v e · l —

第6頁 420723Page 6 420723

曰 修正 e τ t '6.7，773 (1991)。典型的過濾真空電 弧放電法的特色是利用電狐放電形成碳離子沈積，方法是 對上述碳離子施用磁場與電場。然而利用此種方法，不易 在大塊面積獲得均勻的沈積。 圖1示出了利用PECVD方法形成DL C層的先前 技術過程。此種方法使用了由甲烷（亦可使用其他的碳氫 化=物）、氫與氦構成的沈積電漿。然而在此種方法裡， 含氮的根是在分解甲烷的過程內形成，而甲烷是包括在沈 積電漿内’這會致使樣本無可避免地含氫β 發明概述 , 本發明的目的之一係提供一種方法，藉以在大塊面積 形成均勻而大體上無氫的D L C沈積。 在本發明裡，大體無氫&DL C層形成是先沈積一薄 層的DLC層’繼之令其表面與蝕刻電漿曝接。以不將其 稱作逐層沈積法。 ~ 依照本發明，厚度约為1到1 0 0毫微米的〇 L C廣 先/尤積在一塊樣本基片上。然後再令上述D l c層的表 面與餘刻電漿曝接。在後一步驟裡，基片内含有的氫，被 化學熱處理（或蝕刻處理）去除。這會產生大體為無氫的 DLC層。DLC層的特性，可以藉著改變其與蝕刻電漿 的曝接時間而作有利的改變。 任何可作化學蝕刻反應的電漿，皆可作為蝕刻電漿。 钱刻電漿最好可由氟構成，最好是碳氟化物β 依照本發明的另一面’ DLC層是形成在金屬尖上。 附圖說明Modified e τ t '6.7, 773 (1991). A typical filtered vacuum arc discharge method uses electric fox discharge to form carbon ion deposits by applying a magnetic field and an electric field to the above carbon ions. However, with this method, it is not easy to obtain a uniform deposit over a large area. Fig. 1 shows a prior art process for forming a DLC layer using a PECVD method. This method uses a deposition plasma consisting of methane (other hydrocarbons can also be used), hydrogen, and helium. However, in this method, nitrogen-containing roots are formed during the decomposition of methane, and methane is included in the sedimentary plasma. This will cause the sample to inevitably contain hydrogen β. Summary of the invention, one of the objects of the present invention is A method is provided whereby a uniform and substantially hydrogen-free DLC deposit is formed over a large area. In the present invention, a substantially hydrogen-free & DLC layer is formed by first depositing a thin layer of DLC layer 'followed by exposing its surface to an etching plasma. It is not called a layer-by-layer deposition method. ~ According to the present invention, 0 L C of a thickness of about 1 to 100 nm is preliminarily / specifically accumulated on a sample substrate. Then, the surface of the aforementioned D l c layer is exposed to the remaining plasma. In the latter step, the hydrogen contained in the substrate is removed by chemical heat treatment (or etching treatment). This results in a substantially hydrogen-free DLC layer. The characteristics of the DLC layer can be advantageously changed by changing its exposure time to the etching plasma. Any plasma that can be used as a chemical etching reaction can be used as an etching plasma. The coin plasma is preferably composed of fluorine, and most preferably fluorocarbon β. According to the other side of the present invention, the DLC layer is formed on a metal tip. BRIEF DESCRIPTION OF THE DRAWINGS

第7頁 420723 eg. 6. _案號 86108084 ^ 月日_jl^E._ 五、發明說明（4) 熟悉此種技術的人士，參照各附圖即更容易明白本發 明之目的與優點。 圖ΙΑ— 1 B表示出了先前技術利用PECVD方法形成 D L C層的過程。 圖2A— 2 I示出了依照本發明形成DLC層的過程。 圖3示出的沈積DLC膜的傅利葉變換一紅外線吸收（ F R — I R )光譜。 圖4示出了從拖克（Tau c’ s)圖得出的DLC膜光 帶間距。 圖5示出了 D L C膜暗電導率與溫度之間的關係。 圖6示出了 DLC膜的I— E (電流一電場）特性。 圖7示出了 D L C膜因曝接時間產生的特性改變。 圖8是覆以D L C層之鋇場效發射陣列的上視電子顯微鏡 圖。 圖9是覆以D L C層之鋇尖錐的斷面電子顯微鏡圖。 圖1 0示出了覆以DL C層之鋇尖錐與鋇尖錐場效發射陣 列的I — V (電流一電壓）特性。 圖1 1示出了覆以DL C層之鋇尖錐與鋇尖錐場效發射陣 列的佛洛一洛德漢（Fowl e r— No r dhe im) 圖。 圖1 2示出了純鋇場效發射陣列與DL C覆層鋇場效發射 陣列的發射電流波動情形。 較佳實施例之詳細說明 圖2 A顯示與電漿曝接沈積以行D L C覆層的一塊基 材。圖2B顯示利用上述沈積而形成的DLC層（11)Page 7 420723 eg. 6. _ Case No. 86108084 ^ Month Date _jl ^ E._ V. Description of the Invention (4) Those skilled in the art can more easily understand the purpose and advantages of the present invention by referring to the drawings. FIG. 1A-1B shows the process of forming a D L C layer using a PECVD method in the prior art. 2A-2I illustrate a process of forming a DLC layer according to the present invention. FIG. 3 shows a Fourier transform-infrared absorption (F R — IR) spectrum of a deposited DLC film. Fig. 4 shows the DLC film optical band pitch obtained from a Tau c 's diagram. Fig. 5 shows the relationship between the dark conductivity of the D L C film and the temperature. Fig. 6 shows the I-E (current-electric field) characteristics of the DLC film. FIG. 7 shows the change in characteristics of the D L C film due to the exposure time. Fig. 8 is a top-view electron microscope image of a barium field effect emission array coated with a DLC layer. Fig. 9 is a sectional electron microscope image of a barium spike covered with a DLC layer. Fig. 10 shows the I-V (current-voltage) characteristics of a barium-cone and barium-cone field-effect emission array coated with a DLC layer. Fig. 11 shows a Fowl-Nor dhe im diagram of a barium cone and a barium cone field-effect emission array covered with a DLC layer. Fig. 12 shows the emission current fluctuations of the pure barium field emission array and the DLC cladding barium field emission array. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 2A shows a substrate deposited by plasma exposure to form a DLC coating. FIG. 2B shows the DLC layer (11) formed by using the above deposition.

420723 SS 86108084 五、發明說明（5) 。圖2 C顯示 氣的蝕刻電漿 的曝接時間， 利用上述過程 89. §. «I _1420723 SS 86108084 V. Description of the invention (5). Figure 2C shows the exposure time of the gas etching plasma using the above process. 89. §. «I _1

隨後形成另一 層（圖2 E與 二層大體無氫 層即可 第1 0 的D L 在 發明之 與微結 Si : 薄D L 墨C -率施加 用了 C 下表示 得到（ 層D L C層數 用含C 逐層沈 晶S i Η薄層 C層上 C趣。 到基材 Η4 / 出了比 出了在 曝接的 可以有 形成的 層厚度 2 F ) D L C 圖2 Η C層。 ，這些 F4 電 積法， 膜。在 上曝接 曝接藉 使用了 夾。為 H2 / 例的逐 沈積D L C層後，令 情形。在此一步職内 利的改變基材的特今生 大體無氫的第一層彳 約為1 。基材 層的步 )。圖 此一步 D L C 漿作為 被用來 此實施 作化學 以去除 傳統的 了沈積 H e與 層條件 到1 0 〇亳微 與蝕刻電漿曝 驟示於圖2 G 2 I示出了與 驟重複進行即 層合力形成D 餘刻電漿的實 沈積大體無氫 例裡，含氫的 熱處理。然後 弱鍵，主要是 p E C V D 方 D L C層與表 C /He 〇 L c ’改變 。圖2 1 2 ) 米的傳 接，藉 。第二 银刻電 可得到 L C膜 施例裡 的a ~~ 層與含氟 蝕刻電漿 D示出了D L c。統D L c 以得到第 層D L C 漿曝接的 預定數量 〇 ，依照本Then another layer is formed (Figure 2 E and two substantially hydrogen-free layers can be the 10th DL in the invention and the micro junction Si: thin DL ink C-rate application using C is shown below (layer DLC layer number with C Layer-by-layer Shen Jing Si Η Thin layer C on layer C. To the substrate Η4 / shows the thickness of the layer that can be formed during exposure 2 F) DLC Figure 2 Η Layer C. These F4 electric Film method. The film was used in the above process. After the deposition of the DLC layer for each H 2 / case, make the situation. In this step, the first layer of the substrate that is substantially hydrogen-free is changed.彳 is about 1. Step of the substrate layer). In this step, the DLC slurry is used as a chemical to remove the traditional deposition He and layer conditions to 100 μm and the etching plasma exposure is shown in FIG. 2 G 2 I is shown and repeated That is, in the case where the lamination force forms a D-deposited plasma that is substantially hydrogen-free, the hydrogen-containing heat treatment. Then the weak bond, mainly p E C V D square D L C layer and table C / He 〇 L c ′ change. Figure 2 1 2) Transfer of meters, borrow. The second silver engraving can obtain the LC film. In the embodiment, the a ~~ layer and the fluorine-containing etching plasma D show D L c. System D L c to obtain the predetermined amount of D L C slurry exposure 〇

S Η 沈積離子在 C F 4 C ~ Η 法一其 面處理 a 等離子在 η鍵與石 中r f功 ’分別引 條 h 件I沈 h 積丨電漿 飯刻 Η )—~ I loo | Η—-----1--- 0 0S Η deposited ions are treated in CF 4 C ~ 一 method a. Plasma η bond and rf work in the stone are respectively drawn h pieces I Shen h product 丨 plasma rice engraving) — ~ I loo | Η—- ---- 1 --- 0 0

—I Ο · 4 0.45 Η 420723 案號 86108084 月 a 修正 五、發明說明（6) |流速 | H e1 h2 I c h4 I c f4 l·- s c c m 時間（S ) 5 0 5 1 010 0—I Ο · 4 0.45 Η 420723 Case No. 86108084 month a Amendment V. Description of the invention (6) | Flow rate | H e1 h2 I c h4 I c f4 l ·-s c c m Time (S) 5 0 5 1 010 0

I 5 0 I 0 I 0 I 3 0 I0 - 2 0 0 II 5 0 I 0 I 0 I 3 0 I0-2 0 0 I

作 3 0s 間，是 例裡， 曝接時 偏電壓 壓大小 圖 光譜。 稱）與 與 2 換一紅 ，C 一 本發明 D L C 電漿蝕 c c m 得到良 每層厚 間，則 在1 0 程度取 3示出 在分別 s p3 C 9 6 0 外線吸 Η η震 的逐層 層是可 刻處理，Η 〇 D L C 的 好品質的D 度定為5 η 在0到2 0 0 W的固定 決於氣體壓 了 D L C 膜 對應於s ρ3 Η3 (非對稱 αί吸收峰， 收光譜。當 動強度完全 沈積方法， 能的。It takes 30 seconds to show the spectrum of the bias voltage and voltage when exposed. Weighing) and 2 for one red, C for the DLC plasma erosion ccm of the present invention to obtain a good thickness between each layer, then take 3 at a degree of 10 and show that the absorbing of the external line s p3 C 9 6 0 The layer is engravable, and the D of good quality of DLC is set to 5 η. The fixation at 0 to 2 0 W depends on the gas pressure. The DLC film corresponds to s ρ3 Η3 (asymmetric αί absorption peak, and the spectrum is collected. When the dynamic strength is completely deposited, it can.

e與C 每層厚 L C層 m (亳 Os ( r f功 力與r 的傅利 C h3 ( )模式 出現在 C %電 消失。 以P EEach layer of e and C is thick, and the layer of C is m (亳 Os (r f The power and r's Fourier C h3 () mode appear at C% and disappear. Take P E

F“ 的 度與C 的兩個 微米） 秒）之 率時為 f功率 葉變換 對稱） 的2 8 傳統D 漿曝接 這證實 C V D 流速分別為5 0與 拉 離子的曝接時 最重要參數。在此 ，而C F+ 離子的 間。此例測得的自 偏 一紅外線吸收透射 、s p3 C H?(非對 7 0 cm-1' 2 9 2 5 L C層的傅利葉變 時間是2 0 0秒時The degree of F "is two micrometers with C) seconds) and the ratio is f power leaf transformation symmetry) 2 8 traditional D slurry exposure This confirms that the CVD flow rate is 50 and the most important parameter when the ion is exposed. Here, between C F + ions. The measured self-biased infrared absorption transmission, sp 3 CH? (Non-pair 70 cm-1 '2 9 2 5 The Fourier transition time of the LC layer is 200 seconds Time

了一 I 利用依照 法沈積大體無氫的A method for depositing substantially hydrogen-free

第10頁 420723 8ft.,...； _ 案號 86108084_车“月 日__- 五、發明說明（7) 圖4示出了從拖克圖得到的D L C膜光帶間距（E g0# )。此一間距會隨著增加CF4電漿曝接時間，而從1.2 eV增加到1 · 4eV。光帶間距的增加，似乎是由DL C層内石墨因C F4電漿曝接蝕刻階段造成。注意，C 一 C s p3鍵的鍵能（8，68eV)高於C — Cs p2鍵的鍵能 (6.33eV)。因此，C — Cs p2的鍵結與抗鍵結狀 態，存乎於C 一 C s 鍵的内侧。因此s p2鍵的去除，導 -致DLC的間帶距加寬。 圖5示出了 DLC膜暗電導率對溫度的依賴。當將C F4電漿曝接時間增加到2 0 0秒時，D L C膜的導電呈覌 「 活化形式，而活化能則從0 · 2 5 e V增加到〇 · 5 5 e V。這意謂著費密能級（Fermi 1 eve 1)在C F4電漿曝接後移向間距中間，因為大體無氫DLC層的光 帶間距是1 . 4eV，1 . 4eV高於2倍的導電活化能 。傳統D L C層呈現p型行為的特性，而導電活化能約為 0 . 2eV。依照本發明之DLC膜，指示出相對高值的 活化能（0 · 5 5 e V )。 圖6示出了 DLC膜的I— E (電流一電場）特性。 DLC膜的面積與厚度分別是〇 . 9ciri與l〇〇nm。 傳統的DL C膜在高達2 2 ，並無發射的顯示。 然而逐層沈積的DLC膜，顯示出有效果的電子發射一發 射開始領域據發現是1 ，而佛洛一洛德漢（ F owl e r— No r dh e im)公式則說明了發射電 流。 - 大體無氫DL C的電子發射障礙能，根據佛洛一洛德Page 10 420723 8ft., ...; _ Case No. 86108084_Vehicle "Month Day __- V. Description of the Invention (7) Figure 4 shows the DLC film light band spacing (E g0 # ). This distance will increase from 1.2 eV to 1.4 eV as the CF4 plasma exposure time is increased. The increase in optical band spacing seems to be caused by the graphite in the DL C layer due to the C F4 plasma exposure etching stage Note that the bond energy (8,68eV) of the C-Cs p3 bond is higher than the bond energy (6.33eV) of the C-Cs p2 bond. Therefore, the bonding and anti-bonding states of the C-Cs p2 bond are between The inner side of the C-C s bond. Therefore, the removal of the s p2 bond results in a wider interval between DLC. Figure 5 shows the dark conductivity of the DLC film as a function of temperature. When the C F4 plasma is exposed to time When it is increased to 200 seconds, the conductivity of the DLC film is "activated", and the activation energy is increased from 0.25 eV to 0.55 eV. This means the Fermi level (Fermi 1 eve 1) After the C F4 plasma exposure, move to the middle of the pitch, because the optical band spacing of the substantially hydrogen-free DLC layer is 1.4 eV, which is higher than 2 times the activation activation energy. The traditional DLC layer exhibits p-type behavior. Characteristics, and the conduction activation energy is about It is 0.2 eV. The DLC film according to the present invention indicates a relatively high value of activation energy (0.55 e V). FIG. 6 shows the I-E (current-electric field) characteristics of the DLC film. The area and thickness were 0.9 ciri and 100 nm, respectively. The conventional DLC film showed no emission at up to 2 2. However, the DLC film deposited layer by layer showed effective electron emission and the field of emission started. The discovery is 1, and the Fowler-Nordheim formula states the emission current.-The electron emission barrier energy of the substantially hydrogen-free DL C, according to Fowler-Lord

第11頁 420723 - 案號 861 ⑽ 084 五、發明說明（8) ± Λ 曰Page 11 420723-Case No. 861 ⑽ 084 V. Description of the invention (8) ± Λ

漢圖的斜率計算是〇·〇6eV。這指出了DLC膜具有 低的電子發射障礙能。 逐層沈積是在不同的沈積與蝕刻曝接條件下而進行。 c %與H2作DLC沈積的流速分別是6 s c cm與3 s c c m，而作蝕刻電漿處理的c F4流速則定在2 〇 s c c m 圖7示出了依照本發明之 接時間下的I — E (電流一電 LC膜面積定為〇 . 3 cm*。 C F4電漿曝接時間的增加以及 。利用本發明之方法進一步改 開始領域。The slope of the Han chart is calculated as 0.06eV. This indicates that the DLC film has a low electron emission barrier energy. Layer-by-layer deposition is performed under different deposition and etching exposure conditions. The flow rates of c% and H2 for DLC deposition are 6 sc cm and 3 sccm, respectively, and the flow rate of c F4 for etching plasma treatment is set at 20 sccm. Figure 7 shows I — E at the connection time according to the present invention. The area of the current-electricity LC film was set to 0.3 cm *. The increase of the C F4 plasma exposure time and the use of the method of the present invention further changed the field.

在另一個例子裡，鋇尖錐 逐層方法而覆以DLC層。鋇 積在矽基材上，進入直徑1. 在1 0私m的中心，包括了 s 序成長。尖錐相對於柵的高度 的厚度而來決定。在作D l C 20m陶爾（T〇 r r)的壓 厚度約為5 nm的DLC薄層 表面上與其曝接。為了得到厚 C層，乃重複進行DLC沈積 別是大體無.風的D L C層可以 意即沈積5nm的DLC層， DLC層曝接2〇〇秒。 DLC膜在各個Cf4電漿曝 場）特性。在此例内的的D DLC膜的發射電流會隨著 發射門權電場的降低而增加 善D L C的成長，可以減小 場效發射陣列利用本發明之 尖錐被利用電子束蒸發器沈 5 e m的孔内’這些孔分隔 i〇2、！^〇與八1層的依 ’疋根據孔的直徑與絕緣層 層的沈積期間，試片溫度| 力下調整到室溫狀態、一層 先行長成，然後C F4電漿在 度2 〇 nm的大體無氫D]L 與c f4電漿曝接的步驟。特 利用逐層沈積法予以長成， 隨之令C F4電漿與5 n m的In another example, a barium tip cone is covered with a DLC layer-by-layer method. Barium accumulates on the silicon substrate and enters a diameter of 1. In the center of 10 μm, including the s-order growth. The thickness of the cone relative to the height of the grid is determined. It was exposed to a thin layer of DLC with a thickness of about 5 nm made of D l C 20m Tao (Torr). In order to obtain a thick C layer, the DLC deposition is repeated or not. The wind DLC layer can be deposited as a 5nm DLC layer, and the DLC layer is exposed for 200 seconds. DLC film in each Cf4 plasma exposure field) characteristics. The emission current of the D DLC film in this example will increase the growth of the good DLC with the decrease of the emission gate electric field, which can reduce the field effect emission array. The sharp cone of the present invention is used by the electron beam evaporator to sink 5 em Inside the holes' these holes separate i02 ,! ^ 〇 and 801 layer according to the diameter of the hole and the insulation layer during the deposition of the test piece temperature | force adjusted to room temperature, the first layer grows, and then the C F4 plasma at a degree of 20 nm Substantially hydrogen-free D] L and c f4 plasma exposure steps. The layer-by-layer deposition method was used to grow the C F4 plasma with 5 n m

m m處 極~陰 真空環 以利用 射極安· 置開啟 C層的 D L C 典型高 〇 2電 體無氫 D L C 的 9 射陣列的發 開啟電壓是 則是6 5 V 電流，亦從 的鋇尖錐場 1 β A 的 0 7 V，始 L C覆在鋇 兩相對照， 因為D L C L C覆層的The pole-to-cavity vacuum ring at the mm position uses the emitter to install and open the DLC of the C layer. The opening voltage of a 9-electrode array with a typical high-level hydrogen-free DLC is 6 5 V, which is also a barium tip cone. Field 1 β A of 0 7 V, the initial LC is coated on the two phases of barium, because the DLCLC coating

第13頁 89. 6.Page 13 89. 6.

性是利用三極幾 何學來 3 0 〇 生的變 量。電 制。所 接地， η — 〇 )尖錐 尖錐的 8 β m 度約為 的厚度 ’被施以 極偏屬產 境下作測 電腦作控 排，射極 (T U r Μ 〇 (鋇 層的]VI 〇 度是1 · 介層的厚 D L C層 420723 _iS_86108084 五、發明說明（9) 尖錐的電子發射特 塊陽極板置於栅上方1 而陽極與柵電流因為柵 1 0丑陶爾（T 〇 r Γ ) 及電流波動.的試驗，可 行裝置應安排成常見的 ，栅極激勵正電壓令裝 覆以大體無氫D L 於圖8。覆以大體無氫 於圖9 ，圖顯示出尖錐 寬 1 · 5/Wm。熱 Si ，而覆在Mo尖錐的大 n m 。Sex is a variable that uses three poles to learn about 300. Electricity. The ground thickness, η — 〇) is about 8 β m. The thickness of the cone is about 8 '. The thickness is applied to the measurement computer in the extreme production environment. The emitter (TU r Μ 〇 (of barium layer) VI 〇degree is 1. Thick DLC layer of the interlayer 420723 _iS_86108084 V. Description of the invention (9) A tapered electron emission special anode plate is placed above the grid 1 and the anode and grid currents are due to the grid 10 Γ) and current fluctuation. The feasible devices should be arranged as usual. The positive gate excitation voltage causes the device to be covered with substantially hydrogen-free DL as shown in Figure 8. Covered with substantially hydrogen-free as shown in Figure 9, the figure shows a sharp cone width 1 5 / Wm. Hot Si, large nm over Mo tip.

圖10示出了覆以 射陣列與鋇尖錐場效發 錐場效發射陣列的測出 的鋇尖錐場效發射陣列 ，可以得到的最大陽極 “A。而在DLC覆層 時.獲得每一發射器約0 場效發射陣列，則在1 示出只要採用此一將D 顯著地降低工作電壓。 的栅極電壓增加，而且 。請注意，這些鋇與D 作測量。一 V的偏壓。 化是在1 X 流一電壓以 有試驗的進 陽極正電壓 η )。 的結構，示 戴面圖，示 ，栅極通徑 1 · 6 β m 大約為2 0 〇 0尖錐鋇尖錐 射電流電壓特性 8 0 V，而 d L 。除了開啟電壓 1 4 0以A增到 效發射陣列，在 陽極電流，而在 獲得相同的電流 尖錐的構製過程 柵極電流只能隨 的覆層而不能大 鋇尖錐是在相同 場效發 。鋇尖 C覆層 降低外 3 2 0 8 7 V 鋇尖錐 。這顯 ，即可 著施加 幅改變 的條件 420723 案號 86108084 θ 正 五、發明說明（10) ' ~ 下在相同的晶片上成長。電流—電壓特性的修改，因此可 完全歸因到電子發射行為因大體無氳D L C層而致的提昇 =tog A - Β x V是指栅極一 指佛洛一洛德 功函數（〇 及此圖形與橫 率計算出的φ 效增加係數（ 錐的有效妒值 D L C層對降 效發射陣列與 著可變柵極電 與1 2 Β。作 L C覆廣顧尖 錐場效發射陣 尖錐場效發射 圖1 1示出了 DLC覆 尖錐場效發射陣列的佛洛一 射特性，進一步地利用佛洛 1呢（I / V2) 指發射電流； 的交點；Β是 例關係。有效 開啟電壓，以 洛一洛德漢斜 這些尖錐的場 D L C覆層尖 明了大體無氫 著效果《 鋇尖錐場 效發射陣列隨 示於圖1 2 A 實大體無氫D 較傳統純鋇尖 D L C覆層鋇 射陣列的表現 層的鋇尖錐場效發射陣列與鋇 洛德漢圖。兩種尖錐的電子發 —洛德漢方程式予以評估，即 (1000/V)，灰中I是 陰極電壓；log A .是指與垂直轴 漢圖的斜率，斜率與φ5/2呈比 ，從佛洛一洛德漢斜率預估的 座標的截距。比較從鋇尖錐佛 值與鎖金屬的功函數，先得到 4.5eV)。這樣計算出的 是2.6〇eV。這些觀察說 低發射電子所需之功函數的顯 大體無氫D L C覆層鋇尖錐場 壓產生的發射電流波動，分別 中期電流波動的測量，已經證 錐場效發射陣列的發射電流， 列的發射電流來得穩定。所以 陣列的表現優於鋇尖錐場效發Fig. 10 shows the maximum anode "A" that can be obtained with the measured barium cone field-effect emission array coated with the radiation array and barium cone field-effect field emission array, and when DLC is coated. A transmitter with about 0 field-effect emission arrays, shown at 1 as long as this is used, D will significantly reduce the operating voltage. The gate voltage will increase, and. Please note that these barium are measured with D. A V bias The transformation is to apply a positive voltage η to the anode at a current of 1 X. The structure is shown in the wearing diagram, and the gate diameter is 1 · 6 β m. The emission current voltage characteristic is 80 V, and d L. In addition to the turn-on voltage of 1 40, A increases to the effective emission array at the anode current, and the gate current can only follow the structure during the process of obtaining the same current spike. The barium tip cone cannot be formed in the same field effect. The barium tip C coating reduces the outer 3 2 0 8 7 V barium tip cone. This shows that the conditions for changing the amplitude can be applied. 420723 Case number 86108084 θ Positive five, Description of the invention (10) '~ grow on the same wafer. Modification of current-voltage characteristics Therefore, it can be completely attributed to the improvement of the electron emission behavior due to the general absence of the DLC layer = tog A-Β x V refers to the grid-finger-Flode work function (0 and the figure and the abundance calculated The φ efficiency increase coefficient (the effective jealous value of the cone DLC layer for the reduced-efficiency emission array and the variable gate voltage and 1 2 B. For LC coverage, the cone-shaped field-effect emission array is shown in Fig. 1 1 Based on the characteristics of the FLO of the DLC tip-cone field-effect emission array, the FLO 1 (I / V2) is used to refer to the intersection of the emission current; and the B is an example relationship. The effective turn-on voltage is based on the FLO. The oblique field DLC cladding of these oblique cones sharply shows the effect of substantially hydrogen-free. The barium-tip cone field-effect emission array is shown in Fig. 1 A. The substantially hydrogen-free D is compared with the traditional pure barium-tip DLC coating barium emission array. Layered barium cone field-effect emission arrays and barium Lodhan diagrams. The electron emission of the two kinds of cones is evaluated by the Rodham equation, which is (1000 / V). I in the gray is the cathode voltage; log A. The slope with the vertical axis Han diagram, the slope is proportional to φ5 / 2, and it is estimated from the Flo-Rodhan slope The intercept of the coordinates. Comparing the work function of barium tip cone Buddha and the lock metal, we first get 4.5 eV). This calculates 2.60 eV. These observations indicate that the work function required for low emission electrons is substantially hydrogen-free The emission current fluctuations caused by the barium spike field pressure of the DLC coating, and the mid-term current fluctuation measurements, respectively, have proved that the emission current of the cone field effect emission array and the emission current of the column are stable. Therefore, the array performs better than the barium spike field effect. hair

#尖·錐場效發射陣列的電子發射特性與大體無氫D LElectron emission characteristics of # tip · cone field-effect emission array and substantially hydrogen-free D L

第14頁 420^23 6„ Hi 案號86108⑽4_年月日 槔;p 五、發明說明⑴） 一 -- c覆層鋇尖錐場效發射陣列的電子發射特性，已經利用三 極幾何學予以檢驗’據觀察，DL C覆層明顯地提昇了 ^ 子的發射。由於鋇尖錐上的DLC覆層，開啟電壓從8 〇 降為6 5V，而最大陽極電流則從1 4〇昇高到3 20/ζ Α。且大體無氫DL C覆鋇尖雜的發射電流，較傳統純鎖 尖錐場效發射陣列的發射電流為穩定。 考量上述事實，依照本發明之方法而形成的大體無氫.. DLC膜，由於其之硬度、化學惰性、極佳導熱性、大面 積能力、低一場冷發射與發射穩定性等特性，遂可提供一 種有前途的陰極材料’特別是為場效發射陣列。 ： 顯而易見，根據前面的提示，可就本發明作出很多修 改’因此應知道’可按照本專利申請所述以外之方式實現 本發明。Page 14 420 ^ 23 6 „Hi Case No. 86108⑽4_Year Month and Day 槔; p V. Description of the invention ⑴) a-c The electron emission characteristics of the barium-pyramid field-effect array of c-clad layers have been evaluated using tripolar geometry. Inspection 'It was observed that the DLC coating significantly increased the emission of electrons. Due to the DLC coating on the barium cone, the turn-on voltage decreased from 80 to 65 V, and the maximum anode current increased from 140 to 3 20 / ζ Α. And the emission current of the substantially hydrogen-free DL C bar-coated noble is more stable than the emission current of the traditional pure lock-tip cone field-effect emission array. Considering the above facts, substantially no Hydrogen: DLC film, due to its hardness, chemical inertness, excellent thermal conductivity, large area capability, low field cold emission and emission stability, etc., it can provide a promising cathode material, especially for field emission Array .: Obviously, many modifications can be made to the invention according to the previous hints 'so it should be known' that the invention can be implemented in ways other than those described in this patent application.

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Claims (1)

420723420723 86108084 89.6. -i 年月曰 •、Φ誥JL棄丨銘.固」 Ο 1 * —種在基材上形成DLC膜之方法，包含以下步驟 (1 )在基材上生長預定厚度的DL C層； (2 )在DL C層長成後，令D L C層表面與蝕刻離 子曝接。 0 2 ·根據申請專利範圍第1項之方法，其中為了得到預 定厚度的DL C膜，乃在預先成形的DL C層上重 複進行生長與曝接的步驟。 0 3 ·根據申請專利範圍第1項之方法，其中蝕刻電漿包 含了氟氣。 0 4 ·根據申請專利範圍第3項之方'法，其中氟氣是碳氟 化合物。 0 5 ·根據申請專利範圍第4項之方法，其中碳氟化合物 是C F。 0 6 ·根據申請專利範園第1項之方法，其中DLC層的 厚度是1到1 0 0亳微米。 0 7 ·根據申請專利範圍第1項之方法，其中DLC層的 厚度5到2 0毫微米。 0 8 ·根據申請專利範圍第1項之方法，其中為令DL C 層與蝕刻電漿曝接1到2 0 0秒。 0 9 ·根據申請專利範圍第1項之方法，其中為令DL C 層與蝕刻電漿曝接5 0到1 0 0秒。 1 0 ·根據申請專利範圍第1項之方法，其中DLC層乃 是以P E CVD方法使用電漿沈積長成。 1 1 ·根據申請專利範圍第1 0項之方法，其中為生長D LC層用的電漿沈積，包含了 CH4、H2與He86108084 89.6. -I date, Φ • JL discontinuing, solid. 〇 1 * —A method of forming a DLC film on a substrate, including the following steps (1) growing a predetermined thickness of DLC on the substrate (2) After the DLC layer is grown, the surface of the DLC layer is exposed to the etching ions. 0 2 · The method according to item 1 of the scope of patent application, wherein in order to obtain a DLC film of a predetermined thickness, the steps of growth and exposure are repeated on a preformed DLC layer. 0 3 The method according to item 1 of the scope of patent application, wherein the etching plasma contains fluorine gas. 0 4 The method according to item 3 of the scope of patent application, wherein the fluorine gas is a fluorocarbon. 0 5 The method according to item 4 of the patent application, wherein the fluorocarbon is C F. 0 6 The method according to item 1 of the patent application park, wherein the thickness of the DLC layer is 1 to 100 μm. 0 7 The method according to item 1 of the scope of patent application, wherein the thickness of the DLC layer is 5 to 20 nm. 0 8 The method according to item 1 of the scope of patent application, wherein the DLC layer and the etching plasma are exposed for 1 to 200 seconds. 0 9 The method according to item 1 of the scope of patent application, wherein the exposure of the DLC layer to the etching plasma is performed for 50 to 100 seconds. 10 · The method according to item 1 of the scope of patent application, wherein the DLC layer is grown by plasma deposition using a PE CVD method. 1 1 · The method according to item 10 of the scope of patent application, wherein the plasma deposition for growing the D LC layer includes CH4, H2 and He 第16頁 420723 89. 6. -ι _案號 861Q8084_年 月 日___ 六、申請專利範圍 〇 1 2 ·根據申請專利範圍第1 0項之方法，其中之蝕刻電 漿，包含了 CF4 與He。 1 3 _根據申請專利範圍第1項形成之DLC膜。 14·根據申請專利範圍第13項之DLC膜，包含了一 -層（含）以上形成在預先成形的DLC層表面上的 D L C 層。 1 5 ·利用根據申請專利範園第1 3項之D L C膜，作為 場效發射顯示器之場效發射陰極。 Γ 6 · —種場效發射器陣列，包含了利用申請專利範圍第 1項之方法在陣列表面上形成的DL C膜。 1 7 *根據申請專利範圍第1 6項之場效發射器陣列，其 中是為了得到預定厚度的DLC膜，一層（含）以 上的D L C層，形成在預先形成的DL C層表面上 〇 1 8 ·根據申請專利範圍第1 6項之場效發射器陣列，其 中是場效發射器陣列是場效發射顯示器的鋇尖錐場 效發射器陣列。 1 9 ·場效發射顯示器的場效發射陰極，包含了利用申請 專利範圍第1項之方法形成的D L C膜。 2 0 ·根據申請專利範圍第1 9項之場效發射陰極，其中 是為了得到預定厚度的D L C膜，一層（含）以上-的D L C層形成在預先成形的D L C層表面上。Page 16 420723 89. 6. -ι _Case No. 861Q8084_Year Month and Day ___ 6. Application for patent scope 0 1 2 · According to the method of the patent application scope No. 10, the etching plasma includes CF4 and He. 1 3 _ DLC film formed according to item 1 of the scope of patent application. 14. The DLC film according to item 13 of the scope of patent application, comprising one or more DLC layers formed on the surface of the preformed DLC layer. 1 5 · Use the D L C film according to item 13 of the patent application park as the field emission cathode of the field emission display. Γ 6 · —A kind of field-effect emitter array, including a DLC film formed on the surface of the array by the method of the first patent application. 1 7 * The field effect emitter array according to item 16 of the scope of patent application, in order to obtain a DLC film of a predetermined thickness, one or more DLC layers are formed on the surface of the pre-formed DLC layer. The field effect emitter array according to item 16 of the scope of application for patents, where the field effect emitter array is a barium-tip cone field effect emitter array of a field effect emission display. 19 The field-effect cathode of a field-effect display includes a D L C film formed by the method of the first patent application. 20 • The field-effect cathode according to item 19 of the scope of the patent application, in order to obtain a D L C film of a predetermined thickness, one or more D L C layers are formed on the surface of the D L C layer formed in advance. 第17頁Page 17