201111905 、發明說明： 【發明所屬之技術領域】 本發明係有關於一種能夠形成微細201111905, invention description: [Technical field to which the invention pertains] The present invention relates to a method capable of forming a fine
圖案之相位移光罩的製造方法 及相位移光罩。 【先前技術】 在平面齡器，藉由提制案的精確度而使線 寬尺寸更微細，來達成大巾I度提升影像品質。光罩的線寬 精確度、神狀基板料寬精麵變為更微細時，在曝 光時之光罩與基板的_變為更小。因為在平板所使用的 玻璃基板㈣大於3GG麵以上的大尺寸，有玻璃基板的起 伏或表面粗糙度變大，或是容易受到焦點深度的影響之狀 因為玻璃基板係大型尺寸，故平面顯示器的曝光係使 用g射線(436nm)、h射線(他細）、i射線(365nm)的複合波 長’並使用專倍接近式曝光法(例如參照專利文獻1)。 另一方面’在半導體，係使用半色調型相位移光罩作 為達成用以進一步微細化之手法，其係利用ArF(193nm)的 單一波長來進行圖案化(例如參照專利文獻2)。依照該方 法’藉由相位在193nm成為180。來設定光強度成為零之位 置而能夠提升圖案化精確度。又，藉由光強度具有成為零 的位置，能夠將焦點深度設定為較大’能夠謀求提升曝光 條件的緩和或圖案化的產率。 [先前技術文獻] [先前技術] 4/21 201111905 [專利文獻1]特開2007-271720號公報(段落[〇〇31]) [專利文獻2]特開2006-78953號公報(段落[〇〇〇2]、 [0005]) ' 【發明内容】 發明所欲解決之課題 近年來，伴隨著平面顯示器的配線圖案的微細化，對 製造平面顯示器所使用的光罩之微細的線寬精確度要求亦 逐漸提高。但是只縣罩的微細化之曝光條件、顯像條件 等進行研討已逐漸難以因應，開始要求一種用以達成進一 步微細化之新技術。 #於以上情形，本發明之目的係提供一種能夠形成微 細且南精確度的曝光®案之相位移光罩的製造方法、製造 平面顯示器的方法、及相位移光罩。 、 解決課題之手段 為了達成上述目的’本發明的—縣之相位移光罩的 ^造方法係包含將透縣板上的遮光層时化之製程。能 以=透縣板上被覆±述遮光層的方式形成相位移 曰。上述相位移層能夠藉由在含有·以上、_以下 ==乂上、35%以下的氧化性氣體之混合氣體的 =對=刪的纪材來形成。上述相位移層係以 度來形成，成的上“ 罩的達成上述目的，本㈣的-形態之相位移光 罩的狀方料包含在基板上形成級層之製程。在接近 5/21 201111905 二光:層配置有相位移光罩。上述相位移光罩具有相位 夕曰該相位移層係由使其可對於3〇〇讀 任:光線具有⑽。的相位差之氧化氮： ^述3 0 0 上述光阻層係糟由對上述相位移光罩照射 以上、5〇〇nm卩下的複合波長之光線而被曝光。 光罩：U了達成上述目的’本發明的-形態之相位移 二==上遮= 及相位移層。上述遮光層係 層的周D Η 4相移層_成於上述遮光 材料所構成。 的她_化氮化鉻系 包含態之相位移光罩的製造方法，係 。3將透明基板上的遮光層圖案化之製程。在上述透明某 上述遮光層的方式形成相位移層。上述相位移 了在3有4〇%以上、9()%以下的氮化性氣體及_以上、 的氧化性氣體之混合氣體的環境下，濺鍍鉻系材料 ，’巴形成。上述相位移層係以使其可對於300nm以 上以下的波長輯之任—光線具有撕的相位差 來軸。卿成的上述她移層倾81案化成為預 疋圖案。 精由上述方法所製造的相位移光軍係具有使直可對於 3〇〇細以上、500nm以下的波長區域之任mm 的相位差之相位移層。因此，使用該相位移光罩時，藉由 將上述波長區_光_鱗光光線，湘她的反^作 用絲成光強度成為最小的區域，而㈣使曝光圖案更 明。利用此種相位移效果，圖案精確度大幅度地提^，二 6/21 201111905 夠形成微細且高精確度的圖案。藉由使用使在上述波長範 圍之不同波長的光線(例如g射線(436_)、h射線(4〇 i射線複合化之曝光技術，上述效果更顯著。 藉由使用氧化氮化鉻系材料構成上述相位移層 安❶定，形成、具有所需要折射率之賴膜。氣化性氣體小於 40%日…法抑制鈮材的氧化而難以安定地濺 性氣體大於_時，膜中的氧濃度太低而難以得到所= 折射率。另—方面，氧化性氣體小於10%時，膜中的氧:農 =::=所需要折射率。又，氧化性氣體大㈣ ’、 ，’巴材的氧化而難以安定地濺鍍。萨由在上.才、 射率為 ㈣射設錢其可雜i射線具有大 不文此限定，亦能夠以使其可對於 有1:。的相位差之厚度來形成±__=射線具 在此，所謂「大約180。」係意味著 例如180。±1〇。以下。 者180或接近180。， 上述相位移層的厚度可設為 與職h射線的相位差之差異為4〇 =予1射線的相位差 稭此，藉由對於各波長光線 :度。 果，能夠確保形成微細且高精確度的相位移效 亡述處合氣體亦可更含有惰性氣體。、 错此，電衆能夠安定地形成 化性氣體及氧化性氣體_度。 4容易地調整氮 在本發明的-.實施形態之平面顯示器的製造方法’係 7/21 201111905 ^含在基板上形成光阻層之製程 上述相位移光罩具有相== ===30一上、〜下的複合波長區 成。上述総層目之氧化氮化鉻'諸料所構 以上snn 述相位移鮮照射上述3〇〇nm 5GGnm以下賴合波長之L被曝光。 以下光罩係具有使其可對於3〇〇_以上、500nm 下的波長區域之任一光線具有18〇。的相位差 ΐ光=相=上述製造方法時’基於使用上述波長區域 成微㈣精確=圖;夠=提:：:確;’能夠形 顯示器。 回茶祕此夠製造向畫質的平面 作為上述複合波長的光線’例如可使 (436nm)、h 射線⑽nm)、i 射線(365nm)。 凉 杯ίίΓ明的—實施形態之相位移光罩係具備透明基 t遮光層及相位移層。上述遮光層係形成於上述透· 並可對itr移層係形成於上述遮光層的周圍，並由使 =對於_nm以上、·nm町的複合波魏域之任一 先線具有18G。的相位差之氧化氮化鉻系材料所構成。 藉由上述相位移光罩，基於使用上述波長區域的光線 之相位移效果，能夠謀求提升圖案精確 且高精確度之圖案。藉由使用在上述波長範圍 g ^ii(436nm)^h ^^(405nm)>i ^^(365nm)) 歿δ化之曝光技術，上述效果更顯著。 上述相位移層的厚度能夠設為可使賦予 差與賦予g射線的相位差之差異4 40。以下之厚2的相位 8/21 201111905 一定的相位移效 藉此藉由對於各波長光線能夠得到 能夠確保形成微細且高精確度的圖案 【實施方式】 以下，邊參照圖式邊說明本發明的實施形態。 (第1實施形態） θ ,彳’ΤΆ明本發明的—貫施形態之相位移光罩的製造 :之製程圖。本實施形態的相位移光罩係作為例如對平 7不器用玻璃基板之圖案化用光罩而構成。如後述，在 用該光罩之玻璃基板的圖案化上，能夠使用i射線、h射 線及g射線的複合波長作為曝光光線。 首先，在透明基板10上形成遮光層n(圖1(A))。 作為透明基板10，可制透雜及光料方向性優良 2材料，例如可使用石英玻璃基板。透明基板10的大小係 沒有特別限制，可按照使_鮮來進行曝朗基板(例如 平面顯示㈣基板、半導縣板)而適當地選定。在本實施 形態，係使用一邊為3〇〇mm以上的矩形基板，更詳言之， 係使用縱向45〇111111、橫向55〇111„1、厚度8111111的石英基板。 又，藉由研磨透明基板1〇的表面來使透明基板的 表面粗糙度降低。透明基板10的表面粗糙度係例如可以是 50ym以下。藉此，光罩的焦點深度變深，能夠對形成微 細且高精確度的圖案有重大的貢獻。 遮光層11係由金屬鉻或鉻化合物(以下亦稱A ^ 料）’但是不受此限定，金屬矽化合物系材料(例如~M〇Si、 TaSi、TiSi、WSi)或該等的氧化物、氮化物、氧氮化物亦能 夠應用。遮光層11的厚度係沒有特別限制，只要是能夠得 9/21A method of manufacturing a phase shift mask of a pattern and a phase shift mask. [Prior Art] In the flat-aged device, the line width is made finer by the precision of the drawing, and the image quality of the towel is improved by one degree. When the line width of the mask is accurate and the width of the god-shaped substrate material becomes finer, the reticle of the mask and the substrate becomes smaller at the time of exposure. Because the glass substrate (4) used in the flat plate is larger than the larger size than the 3GG surface, the undulation or surface roughness of the glass substrate becomes large, or is susceptible to the depth of focus. Because the glass substrate is large in size, the flat display is The exposure system uses a composite wavelength of g-ray (436 nm), h-ray (thin), and i-ray (365 nm) and uses an exclusive multiple exposure method (for example, refer to Patent Document 1). On the other hand, in the semiconductor, a halftone phase shift mask is used as a method for further miniaturization, which is patterned by a single wavelength of ArF (193 nm) (see, for example, Patent Document 2). According to this method, the phase becomes 180 at 193 nm. To set the light intensity to a position of zero, the patterning accuracy can be improved. Further, by setting the position at which the light intensity is zero, the depth of focus can be set to be large, and it is possible to improve the relaxation of the exposure conditions or the yield of the pattern. [Prior Art] [Prior Art] 4/21 201111905 [Patent Document 1] JP-A-2007-271720 (paragraph [〇〇31]) [Patent Document 2] JP-A-2006-78953 (paragraph [〇〇] 〇2], [0005]) [Problems to be Solved by the Invention] In recent years, with the miniaturization of the wiring pattern of a flat panel display, fine line width accuracy requirements for a photomask used for manufacturing a flat panel display have been demanded. It has also gradually improved. However, it has become difficult to cope with the microscopic exposure conditions and development conditions of the county hood, and a new technology for further miniaturization has been demanded. In the above case, an object of the present invention is to provide a method of manufacturing a phase shift mask capable of forming a fine and south-accurate exposure method, a method of manufacturing a flat panel display, and a phase shift mask. Means for Solving the Problem In order to achieve the above object, the method for producing a phase shift mask of the present invention includes a process for changing the light shielding layer on the plate. The phase shift 曰 can be formed in such a way as to cover the light-shielding layer on the plate. The phase shift layer can be formed by a pair of = = = deleted mixed gas containing oxidizing gas of 5% or less and 5% or less. The phase shifting layer is formed by degrees, and the upper part of the mask is used to achieve the above object, and the shape of the phase shift mask of the present invention is included in the process of forming a layer on the substrate. The approach is close to 5/21 201111905. Two-light: the layer is provided with a phase-shifting reticle. The phase-shifting reticle has a phase eclipse, and the phase-shifting layer is made of nitrogen oxide which has a phase difference of (10). 0 0 The photoresist layer is exposed by irradiating the phase shift mask with light of a composite wavelength of 5 〇〇 nm or less. The mask: U has achieved the above-mentioned object-phase shift of the invention. Two == upper mask = and phase shift layer. The circumference D Η 4 phase shift layer of the light shielding layer layer is formed by the light shielding material. The manufacture of the phase shift mask containing the chrome nitride In the method of patterning a light-shielding layer on a transparent substrate, a phase-shift layer is formed in such a manner as to transparently form the light-shielding layer. The phase is displaced by 3% or more and 9% or less of nitrogen. In the environment of a mixed gas of a chemical gas and an oxidizing gas, splashing A chrome-plated material, 'bar formation. The phase-shift layer is such that it can be used for a wavelength of 300 nm or more. The light has a phase difference of tearing. The above-mentioned pattern of the layer is turned into a pre-turn. The phase shifting optical system manufactured by the above method has a phase shifting layer which makes a phase difference of any mm which is straight into the wavelength region of 3 Å or more and 500 nm or less. Therefore, when the phase shift mask is used, By using the above-mentioned wavelength region _ light _ scale light, Hunan's anti-action filament becomes the region where the light intensity becomes the smallest, and (4) makes the exposure pattern clearer. With this phase shift effect, the pattern accuracy is greatly improved.提^,二6/21 201111905 Enough to form a fine and high-precision pattern by using light rays of different wavelengths in the above wavelength range (for example, g-ray (436_), h-ray (4〇i-ray composite exposure) According to the technique, the above effect is more remarkable. The phase shift layer is formed by using a chromium oxynitride-based material to form a film having a desired refractive index. The gasifying gas is less than 40% of the day. Oxidized and difficult When the splatter gas is larger than _, the oxygen concentration in the film is too low to obtain the refractive index. On the other hand, when the oxidizing gas is less than 10%, the oxygen in the film: agricultural =:: = required refractive index In addition, the oxidizing gas is large (four) ', , 'the oxidation of the material is difficult to settle stably. Sa is in the upper. Only, the rate of incidence (4) shooting money can be miscellaneous i-ray has a large limit, also It is possible to form a ±__= ray having a thickness of a phase difference of 1:, and the term "about 180." means, for example, 180 ± 1 〇. The following is 180 or close to 180. The thickness of the phase shifting layer can be set to be different from the phase difference of the occupational h-ray by 4 〇 = the phase difference of the first ray, by the ray for each wavelength: degree. As a result, it is possible to ensure that a fine and highly accurate phase shift effect is formed, and the gas may further contain an inert gas. In this case, the electric power can stably form a chemical gas and an oxidizing gas. (4) The method of manufacturing a flat panel display according to the present invention is a process for forming a photoresist layer on a substrate. The phase shift mask has a phase =====30 The composite wavelength region of the upper and lower layers is formed. The 総 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 。 。 。 。 。 。 。 。 。 。 。 The following reticle has a light ray having an angle of 18 Å for any of the wavelength regions of 3 Å or more and 500 nm. The phase difference ΐ光=phase=the above manufacturing method' is based on the use of the above-mentioned wavelength region to become micro (four) accurate = map; enough = mention::: indeed; 'can display the display. It is sufficient to produce a light-emitting plane as the light of the above composite wavelength, for example, (436 nm), h-ray (10) nm, and i-ray (365 nm). Cool cups—The phase-shifting reticle of the embodiment is provided with a transparent base t-shielding layer and a phase shifting layer. The light-shielding layer is formed on the permeation layer and is formed around the light-shielding layer in the iteric layer, and has 18G for any of the composite wave domains of _nm or more. The phase difference is composed of a chromium oxide-based material. According to the phase shift mask described above, it is possible to enhance the pattern with high precision and high precision based on the phase shift effect of the light using the above-mentioned wavelength region. The above effect is more remarkable by using an exposure technique in the above wavelength range g ^ ii (436 nm) ^ h ^^ (405 nm) > i ^ (365 nm)) 殁 δ. The thickness of the phase shift layer can be set to a difference 404 between the phase difference between the imparting difference and the g-ray imparted. The following phase 2 of thickness 2/21 201111905 A certain phase shift effect can be obtained by ensuring the formation of a fine and high-precision pattern for each wavelength of light. [Embodiment] Hereinafter, the present invention will be described with reference to the drawings. Implementation form. (First Embodiment) θ , 彳 ' 制 ΤΆ ΤΆ ΤΆ 本 本 本 本 本 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The phase shift mask of the present embodiment is configured as, for example, a pattern mask for a flat glass substrate. As will be described later, in the patterning of the glass substrate using the photomask, a composite wavelength of i-rays, h-rays, and g-rays can be used as the exposure light. First, a light shielding layer n is formed on the transparent substrate 10 (Fig. 1(A)). As the transparent substrate 10, it is possible to obtain a material having excellent permeability and light directionality. For example, a quartz glass substrate can be used. The size of the transparent substrate 10 is not particularly limited, and may be appropriately selected in accordance with the exposure of the substrate (for example, a flat display (four) substrate or a semi-conductive plate). In the present embodiment, a rectangular substrate having a side of 3 mm or more is used, and more specifically, a quartz substrate having a longitudinal direction of 45 〇 111111, a lateral direction of 55 〇 111 „1, and a thickness of 8111111 is used. Further, by polishing a transparent substrate The surface roughness of the transparent substrate is reduced by a surface of 1 Å. The surface roughness of the transparent substrate 10 can be, for example, 50 μm or less. Thereby, the depth of focus of the reticle is deepened, and it is possible to form a fine and highly precise pattern. Significant contribution. The light-shielding layer 11 is made of a metal chromium or chromium compound (hereinafter also referred to as A ^ material) but is not limited thereto, and a metal-ruthenium compound-based material (for example, ~M〇Si, TaSi, TiSi, WSi) or the like Oxides, nitrides, and oxynitrides can also be used. The thickness of the light shielding layer 11 is not particularly limited as long as it can obtain 9/21
• I • I 201111905 =::=光學濃度之厚度(例如800〜2〇〇〇A)即可。成 膜法(αΓό°；ΤΓΙ子射線蒸鍍法、雷射蒸鍍法、原子層成 子輔助购，特別是大型基板的: 用C歲鑛法能約進行 隨後，在透光層U卜❹上 W生優良之成膜。 12可以是正型亦可成ί阻層12(圖1(Β))。光阻層 亦可使用乾=。°可使用液狀光阻作為光阻層 η上=1藉由將光阻層12進行曝光或顯像，而在遮光層 案來決定適當的形狀。％ %糾照遮先層11 _刻圖 透明1:遮f層11兹刻成為預定圖案。藉此，能夠在 形成被圖案化成為預定形狀之遮光層 特別iif二？蝕刻製程能夠應用濕式蝕刻或乾式蝕刻， 面内=Μ ▲ 型時’藉由採用乾式⑽法，能夠實現 面内均勻性向的姓刻處理。 李射 層11的_賴_當地藝，栽層η係鉻 2科時’例如能夠使用石肖酸飾銨及過氣酸的水溶液。因 2钱刻液係與玻璃基板的選擇比高，在遮光層η的圖案 夠保護透明基板1G。另—方面，遮光層11係由金 、匕物系材枓所構成時，敍刻液例如可使用氟化氣録。 遮光層11P1的圖案化後’係除去光阻圖案1迚1(圖 ):除去光_案12P1係例如可使賴氧化鈉水溶液。 祐2=形成她移層13。相細113細遮光層I1P1 被设透明基板1G上的方式形成(圖1(F))。 10/21 201111905 作為相位移層13的成膜方法，能夠應用電子射線(EB) 蒸鍍法、雷射蒸鍍法、原子層成膜(ALD)法、離子輔助濺鍍 法等，特別是大型基板的情況下，採用DC濺鍍法能夠進行 膜厚度均勻性優良之成膜。又，不受DC濺鍍法限定，亦能 夠應用AC濺鑛法或RF錢錢法。 相位移層13係由鉻系材料所構成。特別是本實施形 態’相位移層13係由氧化氮化鉻所構成。若採用鉻系材料， 特別是在大型基板上，能夠得到良好的圖案化性。又，不 受鉻系材料限定，亦可使用例如MoSi、TaSi、WSi、、• I • I 201111905 =::=The thickness of the optical density (for example, 800~2〇〇〇A). Film formation method (αΓό°; scorpion ray evaporation method, laser evaporation method, atomic layer sub-assisted purchase, especially large-scale substrate: using C-year-old mineral method can be carried out subsequently, on the light-transmissive layer U W is excellent in film formation. 12 can be positive or can be formed into a resist layer 12 (Fig. 1 (Β)). The photoresist layer can also be used dry = ° ° liquid photoresist can be used as the photoresist layer η upper = 1 The appropriate shape is determined in the light-shielding layer by exposing or developing the photoresist layer 12. %% of the masking layer 11 _ patterning transparent 1: the masking layer 11 is engraved into a predetermined pattern. It is possible to form a light-shielding layer that is patterned into a predetermined shape, in particular, if the etching process can apply wet etching or dry etching, and in-plane = ▲ ▲ type, the in-plane uniformity can be achieved by using the dry (10) method. The surname is processed. The lithography layer 11 of the _ _ _ local art, planting layer η chrome 2 branch time 'for example, can use the aqueous solution of ammonium sulphate and peroxyacid. Because of the choice of 2 money liquid system and glass substrate The ratio is high, and the pattern of the light shielding layer η is sufficient to protect the transparent substrate 1G. On the other hand, the light shielding layer 11 is made of gold and a metal material. In the case of the composition, for example, a fluorinated gas can be used. After the patterning of the light-shielding layer 11P1, the photoresist pattern 1迚1 is removed (Fig.): The light is removed. For example, the 12P1 system can be used to make an aqueous solution of sodium sulphate. 2 = forming her migration layer 13. The phase 113 thin light shielding layer I1P1 is formed on the transparent substrate 1G (Fig. 1 (F)). 10/21 201111905 As a film formation method of the phase shift layer 13, an electron beam can be applied. (EB) vapor deposition method, laser vapor deposition method, atomic layer formation (ALD) method, ion-assisted sputtering method, etc., in particular, in the case of a large substrate, DC sputtering can be used to achieve uniform film thickness uniformity. Further, the AC sputtering method or the RF money method can be applied without being limited by the DC sputtering method. The phase shift layer 13 is composed of a chromium-based material. In particular, the phase shift layer 13 of the present embodiment is Chromium oxynitride is used. When a chromium-based material is used, particularly on a large substrate, good patterning properties can be obtained. Further, it is not limited by the chromium-based material, and for example, MoSi, TaSi, WSi, or
NiSi、CGSi、ZrSi、NbSi、TiSi或該等的化合物等的金屬石夕 化物系材料。而且，亦可使用Ti、Ni或該等的化合物 等。 使用濺鍍法形成由氧化氮化鉻所構成之相位移層13 時’能夠使用氮化性氣體及氧化性氣體的混合氣體或情性 氣體、氮化性氣體及氧化性氣體的混合氣體作為製程氣 體，成膜壓力係例如可以是〇.1Pa〜〇 5Pa。 礼玍軋媸万面係包含c〇、c〇2、N〇、N2〇、N〇2、 〇2等。在氮化性氣體方面係包含]^0、乂〇、^^〇2、沁等。 作為惰性氣體，係使用Ar、He、Xe #，典型地2，^使用A metal-based material such as NiSi, CGSi, ZrSi, NbSi, TiSi or the like. Further, Ti, Ni, or the like may be used. When the phase shift layer 13 composed of chromium oxynitride is formed by sputtering, 'a mixed gas of a nitriding gas and an oxidizing gas or a mixed gas of an inert gas, a nitriding gas, and an oxidizing gas can be used as a process. The gas, film forming pressure system may be, for example, 〇1 Pa to 〇5 Pa. The ritual rolling mill includes c〇, c〇2, N〇, N2〇, N〇2, and 〇2. In terms of nitriding gas, it includes ]^0, 乂〇, ^^〇2, 沁, and the like. As an inert gas, Ar, He, Xe #, typically 2, ^ are used.
Ar。又’在上述混合氣體亦可更包含Ch4等的碳化性氣體。 混合氣體中的氮化性氣體及氧化性氣體的流量（濃 就決定相位移層13的光學性質(透射率、折射率等)而 要1參數。在本實獅態’能触氮化性氣體漢度 為40/。以上、90%以下且氧化性氣體的濃度為·以上、 35%以下的條件來調整混合氣體。藉由調整氣體條件，能夠 將相位移層U崎射率、透射率、反㈣、錢等最佳化。 11/21 201111905 安定地_ ===無法抑制1巴材的氧化而難以 太低而難以得到;要:射:於9〇%時，膜中的氧濃度 =。::要:二 難以安定地=氧體大於35%時，無法抑制靖的氧化而 300-3〇〇nm ^ ' 度。-祕具有觸。_位差之厚 未透射相位移> n相位差之光線’藉由相位反轉且藉由與 光線之干擾作用，能夠消滅該光線的 小(例如im 效果’因為能夠形成光強度成為最 成L田圖1£域’曝光圖案變為鮮明，能夠高精細度地形 在本實施形態，上述波長區域 線(4°一'一㈣的二色光; 形成相位移層的目先=賦長的相位差之厚度來 射ί 讀可叹丨射線、h ㈣亦可以是料以外的波長區域之 微細的圖案^反轉相位的光線之波長越短時，越能夠形成 在本實施形態’能夠以使賦予i射線的相位差與賦 ;線的相位差之差異為4G。町之厚度來形成相位移層 。猎此，對於各波長的光線能夠得到—定的她移效果。 例如㈣以對於上述複合波長中之中間波長區域亦即h射 線賦予大約刚。(180。±10。)的相位差之膜厚度來形成相位 移層13。藉此，因為對於i射線及g射線的任一者亦能夠 12/21 201111905 賦予接近_。_位差’對各自的光線城夠得到同樣的 相位移效果。 相位移層13的膜厚度以在透明基板1()的面内均句為 ί。在本實施形態’係對於g射線、h射線及i射線的各自 早一波長級’以基板φ内之仙差的差分為2G。以下的膜 厚絲形成相位移層13。該相位差的差分大於20。時，由 於在複合波長之光強度重疊效果，會使光強度的強弱變 小’致使®案精確度低落。藉由使上勒位差的差分在γ 以下、進而10。以下，能夠謀求進—步提升圖案精確度。 相位移層13的透射率係例如對於i射線可以是1%以 上、20。/。以下的範圍。透射率小於1%時，因為難以得到充 分的相位移絲，雜冑精確度地賴 困難。又’透射率大於聰時，成膜速度低落， 性變差。在上述範圍，透射率可以進而是2%以上、15%以 下的範圍。而且’在上述範圍’透射率可以是3%以上、1〇% 才夕曰^ w久扪千诉例如4〇%以下。藉此，使用Ar. Further, the mixed gas may further contain a carbonized gas such as Ch4. The flow rate of the nitriding gas and the oxidizing gas in the mixed gas (concentration determines the optical properties (transmittance, refractive index, etc.) of the phase shifting layer 13 and takes one parameter. In the present lion state, it is capable of nitriding gas. The mixed gas is adjusted under the conditions of 40% or more and 90% or less and the concentration of the oxidizing gas is 5% or more and 35% or less. By adjusting the gas conditions, the phase shifting layer U can be used, the transmittance, and the transmittance. Anti-(four), money, etc. 11/21 201111905 Stability _ === can not inhibit the oxidation of 1 bar material and it is difficult to get too low and difficult to obtain; to: shoot: at 9〇%, the oxygen concentration in the film = :::2: It is difficult to stabilize = when the oxygen is greater than 35%, it can not inhibit the oxidation of Jing and 300-3〇〇nm ^ ' degrees. - Secret has a touch. _ Displacement thickness of the non-transmissive phase shift > n The phase difference light' can be eliminated by the phase inversion and by the interference with the light (for example, the im effect 'because the light intensity can be formed to become the most L-field map> the exposure pattern becomes distinct The high-definition topography of the present embodiment, the wavelength region line (4°-one (four) dichromatic light; shape The phase of the phase shifting layer is the thickness of the phase difference of the length of the phase. The thickness of the phase difference is read. The reading of the sinus ray, h (four) or the fine pattern of the wavelength region other than the material. In the present embodiment, it is possible to form a phase shift layer by making the difference between the phase difference between the phase difference of the i-ray and the line of the electron beam 4G. The thickness of the line can be used to form a phase shift layer. She shifts the effect. For example, (4) the phase shift layer 13 is formed by imparting a film thickness of a phase difference of about (180 ± 0.01) to the intermediate wavelength region in the above composite wavelength, that is, the h-ray. Any of the ray and the g-ray can also be given 12/21 201111905 to give close _. _ dislocations to the same ray ray to obtain the same phase shift effect. The film thickness of the phase shift layer 13 is on the transparent substrate 1 () The in-plane average sentence is ί. In the present embodiment, the difference between the difference in the substrate φ for each of the g-ray, h-ray, and i-ray is 2 G. The following film thickness forms a phase shift layer. 13. The difference of the phase difference is greater than 20. Due to the overlapping effect of the light intensity at the composite wavelength, the intensity of the light intensity is reduced, which results in a decrease in the accuracy of the ® method. By making the difference in the upper difference of the gamma below γ and further below 10, it is possible to further improve. The accuracy of the pattern. The transmittance of the phase shift layer 13 can be, for example, 1% or more and 20% or less for the i-ray. When the transmittance is less than 1%, the miscibility is difficult because a sufficient phase shifting wire is difficult to obtain. In the above range, the transmittance may further be in the range of 2% or more and 15% or less. In the above range, the transmittance may be 3% or more, 1〇% 曰 曰 w ^ w 扪 诉 诉 例如 例如 诉 诉 诉 诉 诉 诉 诉 诉 诉 诉Use this
才目”光罩之被處理基板(平面顯示器或半導體基板)在IThe substrate of the mask (planar display or semiconductor substrate) is in I
不容絲成疊案⑽⑽pattern)而能夠確伴 好的圖案精確度。 《=*幻崎俅I 相位移層13的透射率及反射率㈣藉由成 地調整。依照上述的混合觸 射線為丨/°以上、鳩以下的透射率及40%以下的反射率c 13的厚度㈣在可彳㈣上制絲特性 圍而適*地妓，财之，藉由將她 化’能夠得到上述的光學。例如採用上述條 13/21 201111905 ，匕光學特性之相位移層13的膜厚度係例如論爪以 ^ 3〇nm以下。在該範圍，相位移層13的膜厚度可以進 而疋llOnm以上、I25nm以下的範圍。 舉出_個财’在賴軸_的混合韻的流量比 二Ar. N2 C02 2.5 . 6 . 1.5 ’且將膜厚度設為1Mnm時， 能夠使i射線之透射率為5.5%，丨射線之相位差為π。， 並使g射線之相位差為146。。又，將混合氣體的流量比設 為Ar . N2 · C02=2 : 7 :丨’且將膜厚度設為i2〇nm時，能 夠使i射線之透射率為4.8%，丨射線之相位差為185。，並 使g射線之相位差為153。。 圖2係顯示相位移層13成膜時的成膜條件與各波長成 分的相位差與透射率的關係之實驗結果。本例係使 用A作為氮化性氣體，使用c〇2作為氧化性氣體及使用 Ar作為惰性氣體。成膜壓力為〇 2pa。 如圖2所不，在含有4〇%以上'9〇%以下的氣化性氣體 及10%以上、35%以下的氧化性氣體之混合氣體的條件(試 ϋΐ〜5)。’在30〇nm以上、5()()nm以下的波長區域可使 其具有180°的相位差。又，藉由以對於i射線能夠賦予⑽。 ±10的相位差之厚度來形成相位移層，能夠將丨射線與g 射線之間的相位差之差異抑制為4〇。(3〇。）以下。而且，能 夠將i射線的透射率抑制為1%以上、1〇%以下。 相對於此，在氮化性氣體為大於9〇%且氧化性氣體為 小於10%的條件(試樣Νο·6)下，膜的氧化度小，即便增加 膜厚度亦無法得到必要的相位差及透射率。又，在氧化性 氣體大於35%的條件(試樣Ν〇 7)及只有氧化性氣體的環境 條件(試樣Νο.8)下，膜的氧化度變為太大而無法得到必要 14/21 201111905 的相位差，且無法抑制透射率的上升。 由於崎絲魄切展，賴n#條件下， 膜厚度。 民而無法侍到充分的 接著，在相位移層13上形成光 β 14 of L7 0 τ *ι) -λ- g 14(圖 1(G))。光阻 層Η可以疋正型亦可以是負 元阻 阻。 歧層14可使用液狀光 柯取竹尤阻層14曝光及顯像， :3/形成光阻圖案_(圖_。光阻圖；MP= 13 6_光罩之功能’能夠按照相位移/13的 餘刻圖案來決定適當的形^ Μ 13的 接著，將相位移層13㈣成為财的_ 爾酿糊概之9相位 刻法相^^3^=製程能夠___法或乾式餘 夠實現面二板係大型時，藉由採用濕式蝕刻法，能 多勺貝見面内均勻性高的蝕刻處理。 離’ Γ的^刻液能夠適當地選擇，在本實施形 二=Γ 録及過氣酸的水溶液。因為該㈣液 基板的選擇比高，在相位移層13的圖案 保蠖基板10。 在相位移層13的圖案化後，係除去光阻圖案剛（圖 ())。除去光阻圖案剛係例如能使用氫氧化納水溶液。 t上述進行，_製造本實郷態之相位移光罩卜藉 ，貫施形態的相位移光罩卜能夠在遮光層11P1的周 圍’形成上述構成的相位移層13P1。藉此，在對使用300nm 以上、5〇0nm以下的波長區域的光線之被曝光基板形成曝 15/21 201111905 光圖案時，能夠謀求提升基於相位移效果之圖案精確度， 而可形成微細且高精確度的圖案。特別是依照本實ς形 態’藉由使用在上述波長範圍使不同波長的光線仏射線、匕 射線及i射線)複合化之曝光技術，變為更顯著。 以下，5兒明本實施形態之使用相位移光罩丨 示器的製造方法。 、，貝 、、首先，在形成有絕緣層及配線層之玻璃基板的表面形 成光阻層。光阻層的形成係例如可使用旋轉塗布器。光阻 層係施加加熱處理(烘烤)後，施行使用相位移光罩°〗之曝光 處理。在曝光製程’係在接近光阻層配置相位移光罩1。然 後，隔著相位移光罩1對基板表面照射30〇nm以上、5〇〇二 =下的複合波長。在本實施形態，上述波長的光線能夠使 g射線、h射線及丨射線n能夠將對應相位移 1的光罩圖案而成之曝光圖案轉印至光阻層。 依照本實_® ’相位移光罩1係具有使其可對於 300nm以上、500nm以下的波長區域之任一光線具有180、。 的相位差之相位移層13P1。因此，依照上述製造方法 =使用上述波長區域的光線，能觸求基於相位差效果^ ’並且因為加深焦點深度，能夠形_細 且冋精確度的圖案。藉此’能夠製造高畫質的平面顯示器。 依照本發明者等的實驗，使用未具有該相位移層 t曝光時’對於目標線寬(2_會產生30%以上的圖案 見偏移’但是使用本實施形態的相位移光罩而曝光時，墟 認能夠將偏移抑制為7%左右。 J、光夺確 (第2實施形態） 圖3係說明本發明的第2實施形態的相位移光罩的製 16/21 201111905 造=之製㈣。又，在圖3，對與圖！對應部分係附加同 一付唬，並省略其詳細的說明。 2施雜物缚光罩2(圖3_在弱部具有位 ，>、之對準標記，且該對準標記係使用遮光層贈形 成。以下，說明相位移光罩2的製造方法。 々、由1先，在透明基板1〇上形成遮光層11((圖3(A))。隨後， 、’、’層11上形成光阻層12(圖3))。光阻層12可以是正 以μ型°隨後’#由將光阻層12曝光及顯像，而 月b »遮光層11上形成光阻圖案12P2(圖3(C))。 光阻圖案12P2係作為遮光層u賴刻光罩之功能， =按遮光層11的1爛圖案來決定適#的形狀。圖3(〇 =不為了在基板1G的周緣預定範圍内使遮 成光阻圖案12P2之例子。 ’將遮光層U钱刻成為預定的圖案形狀。藉此， 透明基板1G上’形成被圖案化成為狀形狀之遮光 遮光層_的圖案化後，除去光阻圖ί 納水|容圖夜3⑹）。光阻圖案12ρ2的除去係例如可使用氣氧化 ω上13餘透明基板 係由氧化氮化鉻系材料所 士处机 叶W構成，且使用DC濺鍍法成膜。此 二杨夠f用氮化性氣體及氧化性氣體之混合氣體或惰性氣 :位移層13細與增丨實施形=:=:形 接著，在相位移層13上形成級層丨4((圖3(G))。隨 17/21 201111905 後’藉由將光阻層14曝光及顯像， 上形成光阻圖案刚(圖3⑽。光 ^ )移層13 2 13的輪罩之功能，能夠按照 圖案來決定適當的形狀。 s的蝕刻 能夠移層13麵成為預定的圖案形狀。藉此， 移層ΐ3Ρ2‘α^形成被圖案化成為預定形狀之相位 光_=);= 氣氧化納水溶圖案14Ρ2係例如能使用 如以上進行，能夠製造本實施形態之相位移光罩2。藉 2貫施形態的相位移光罩2，因為對準標記能夠以遮光層 2形成，光學性辨識對準標記變為容易，能夠高精確度 地^位置。本實施形態能夠與上述的第】實施形態组合 而實施。 匕σ 4又’相位移層13能夠使其作為半色調(半透射層)之功 能。此時’能夠使透過與未透過她移層13的光線具有曝 光量差異。 以上，說明了本發明的實施形態，當然，本發明不受 此限定，基於本發明的技術思想能夠進行各種變形。 例如在以上的實施形態，係在遮光層的圖案化後進行 相位移層的賴及®案化，但是不受此限定，亦可以在相 位移層的成膜及瞧化後，進行遮光層的成膜及圖案化。 亦即，能夠變更遮光層及相位移層的積層順序。 又，在以上的實施形態，係將遮光層η在基板10的 全面成膜後，藉由將必要部位蝕刻來形成遮光層11Ρ1、 11Ρ2，但是亦可以形成遮光層11ρι、ηρ2的形成區域為開 18/21 201111905 口之光阻圖案後，形成遮光層u來代替。形成遮光層u 後’藉由除去上述級圖案而能夠在必要區域形成遮光層 IIP卜11P2(剝離法）。 【圖式簡單說明】 圖1係說明本發明的第丨實施態樣之相位移光罩的製 造方法之製程圖。 、 圖2係顯示上述相位移光罩的相位移層的成膜條件與 光學特性的關係之實驗結果。 ' 圖3係說明本發明的第2實施態樣之相位移光罩的製 造方法之製程圖。 、 【主要元件符號說明】 1 '2 相位移光罩 10 透明基板 11、11P1、11P2 遮光層 12 光阻層 12P1 ' 12P2 光阻圖案 13、13P1、13P2相位移層 14 光阻層 14P1 ' 14P2 光阻圖案 19/21It is not allowed to be stacked (10) (10) pattern) and can be accompanied by good pattern accuracy. The transmittance and reflectance (4) of the "=* magical 俅I phase shifting layer 13 are adjusted by the ground. According to the above-mentioned mixed contact ray, the transmittance of 丨/° or more, the transmittance below 鸠 and the thickness of the reflectance c 13 of 40% or less (4) are suitable for the yarn-making characteristics of the 彳 (4), and She can't get the above optics. For example, in the above-mentioned article 13/21 201111905, the film thickness of the phase shift layer 13 of the optical property is, for example, less than ^ 3 〇 nm. In this range, the film thickness of the phase shift layer 13 may be in the range of llOnm or more and I25nm or less. The flow rate of the mixed rhyme of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The phase difference is π. And make the phase difference of the g-rays 146. . Further, when the flow rate ratio of the mixed gas is Ar. N2 · C02 = 2 : 7 : 丨 ' and the film thickness is i2 〇 nm, the transmittance of the i-ray can be made 4.8%, and the phase difference of the x-ray is 185. And make the phase difference of the g-rays 153. . Fig. 2 is an experimental result showing the relationship between the film formation conditions and the phase difference of each wavelength component and the transmittance when the phase shift layer 13 is formed. In this example, A is used as the nitriding gas, c〇2 is used as the oxidizing gas, and Ar is used as the inert gas. The film formation pressure is 〇 2pa. As shown in Fig. 2, the gas is contained in a gas mixture of 4% by volume or more and 9% by volume or less and a mixed gas of 10% or more and 35% or less of oxidizing gas (test ϋΐ 5). The wavelength region of 30 〇 nm or more and 5 () () nm or less can have a phase difference of 180°. Further, by giving (10) to the i-ray. The thickness of the phase difference of ±10 forms a phase shift layer, and the difference in phase difference between the x-ray and the g-ray can be suppressed to 4 〇. (3〇.) The following. Further, the transmittance of the i-ray can be suppressed to 1% or more and 1% or less. On the other hand, in the condition that the nitriding gas is more than 9% by mass and the oxidizing gas is less than 10% (sample Νο·6), the degree of oxidation of the film is small, and even if the film thickness is increased, the necessary phase difference cannot be obtained. And transmittance. Further, under the conditions of the oxidizing gas of more than 35% (sample Ν〇7) and the environmental conditions of only the oxidizing gas (sample Νο. 8), the degree of oxidation of the film became too large to obtain the necessary 14/21. The phase difference of 201111905 does not suppress the increase in transmittance. Due to the smashing exhibition, Lai N# conditions, film thickness. The person cannot serve enough. Next, light β 14 of L7 0 τ *ι) -λ- g 14 is formed on the phase shift layer 13 (Fig. 1(G)). The photoresist layer can be either positive or negative. The disambiguation layer 14 can be exposed and developed using a liquid photo-resistance layer 14 : : 3 / forming a photoresist pattern _ (Fig. _. Photoresist pattern; MP = 13 6 _ reticle function can be phase-shifted /13 of the remaining pattern to determine the appropriate shape ^ Μ 13 followed by the phase shift layer 13 (four) becomes a wealth of _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ When the two-face plate system is large, by using the wet etching method, it is possible to use a plurality of spoons to meet the etching process with high uniformity in the plane. The liquid from the 'Γ can be appropriately selected, and in this embodiment, the second form is recorded. The aqueous solution of the gas is too high. Since the selection ratio of the (four) liquid substrate is high, the substrate 10 is protected by the pattern of the phase shift layer 13. After the patterning of the phase shift layer 13, the photoresist pattern is removed (Fig. For example, an aqueous solution of sodium hydroxide can be used for the removal of the photoresist pattern. t. The above-mentioned phase-shift mask of the actual state is formed, and the phase-shift mask of the form can be formed around the light-shielding layer 11P1. The phase shift layer 13P1 having the above configuration, whereby light rays in a wavelength region of 300 nm or more and 5 Å 0 nm or less are used. When the exposed substrate forms an exposed 15/21 201111905 light pattern, it is possible to improve the pattern accuracy based on the phase shift effect, and to form a fine and high-precision pattern. In particular, according to the present embodiment, by using the above wavelength range The exposure technique of combining light rays, xenon rays, and i-rays of different wavelengths becomes more remarkable. Hereinafter, a method of manufacturing a phase shift mask using the embodiment of the present invention will be described. First, a photoresist layer is formed on the surface of the glass substrate on which the insulating layer and the wiring layer are formed. The formation of the photoresist layer can be, for example, a spin coater. After the photoresist layer is subjected to heat treatment (baking), exposure treatment using a phase shift mask is performed. In the exposure process, the phase shift mask 1 is disposed adjacent to the photoresist layer. Then, the surface of the substrate is irradiated with a composite wavelength of 30 〇 nm or more and 5 〇〇 2 = under the phase shift mask 1. In the present embodiment, the light of the above-mentioned wavelength enables the g-ray, the h-ray, and the x-ray n to transfer the exposure pattern corresponding to the mask pattern of the phase shift 1 to the photoresist layer. According to the present invention, the phase shift mask 1 has a light source of 180 for any wavelength region of 300 nm or more and 500 nm or less. The phase difference of the phase shift layer 13P1. Therefore, according to the above manufacturing method = using the light of the above-mentioned wavelength region, it is possible to draw a pattern based on the phase difference effect ^' and because the depth of focus is deepened, it is possible to form a pattern of fineness and precision. By this, it is possible to manufacture a high-quality flat panel display. According to experiments by the inventors of the present invention, when the exposure is not performed with the phase shift layer t, 'the target line width (2_ will produce a pattern of 30% or more offset) but the exposure is performed using the phase shift mask of the present embodiment. In the second embodiment, the phase shift mask of the second embodiment of the present invention is manufactured by the method of making a phase shift mask of the second embodiment of the present invention. (4) In addition, in Fig. 3, the same reference numerals are attached to the corresponding parts of Fig. 3, and the detailed description thereof will be omitted. 2 The splicing mask 2 (Fig. 3_ has a bit in the weak portion, > The alignment mark is formed using a light shielding layer. Hereinafter, a method of manufacturing the phase shift mask 2 will be described. 々 First, a light shielding layer 11 is formed on the transparent substrate 1 (FIG. 3(A) Then, the photoresist layer 12 (Fig. 3) is formed on the ', ' layer 11. The photoresist layer 12 may be positively exposed to μ and then '# by exposing and developing the photoresist layer 12, and the month b » A photoresist pattern 12P2 is formed on the light shielding layer 11 (Fig. 3(C)). The photoresist pattern 12P2 functions as a light shielding layer, and the light shielding layer is used as a light shielding layer. Fig. 3 (〇 = an example in which the photoresist pattern 12P2 is not formed in a predetermined range around the periphery of the substrate 1G. 'The light shielding layer U is engraved into a predetermined pattern shape. Thereby, the transparent substrate 1G After the patterning of the light-shielding layer _ which is patterned into a shape is formed, the photoresist pattern is removed, and the pattern of the photoresist pattern 12ρ2 is removed. For example, more than 13 transparent layers of gas oxidization ω can be used. The substrate is composed of a machine W of a chromium oxynitride-based material, and is formed by a DC sputtering method. The second gas is a mixed gas of a nitriding gas and an oxidizing gas or an inert gas: a displacement layer 13 Fine and enhanced implementation form =:=: shape Next, a level layer 丨4 is formed on the phase shift layer 13 ((Fig. 3(G)). With 17/21 201111905, 'by exposing the photoresist layer 14 and displaying For example, the function of the wheel cover on which the photoresist pattern is formed (Fig. 3 (10). Light) is shifted by the layer 13 2 13, and an appropriate shape can be determined according to the pattern. The etching of s can shift the surface of the layer 13 into a predetermined pattern shape. Thus, the shift layer ΐ3Ρ2'α^ forms a phase light that is patterned into a predetermined shape _=); For example, the phase shift mask 2 of the present embodiment can be manufactured by using the above method. The phase shift mask 2 of the embodiment can be formed by the light shielding layer 2, and the alignment mark can be optically recognized. It is easy to perform the position with high precision. This embodiment can be implemented in combination with the above-described embodiment. The 匕σ 4 and the 'phase shift layer 13 can function as a halftone (semi-transmissive layer). In this case, the difference in exposure amount between the light transmitted and the light-transmissive layer 13 can be made. The embodiment of the present invention has been described above. Of course, the present invention is not limited thereto, and various modifications can be made based on the technical idea of the present invention. For example, in the above embodiment, the phase shift layer is formed after the patterning of the light shielding layer. However, the present invention is not limited thereto, and the light shielding layer may be formed after the film formation and deuteration of the phase shift layer. Film formation and patterning. That is, the order of lamination of the light shielding layer and the phase shift layer can be changed. Further, in the above embodiment, the light shielding layer η is formed by etching the necessary portions after the entire surface of the substrate 10 is formed, but the light shielding layers 11ρ1 and ηρ2 may be formed. 18/21 201111905 After the photoresist pattern of the mouth, a light-shielding layer u is formed instead. After the light-shielding layer u is formed, the light-shielding layer IIP 11P2 (peeling method) can be formed in a necessary region by removing the above-described pattern. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process diagram for explaining a method of manufacturing a phase shift mask according to a third embodiment of the present invention. Fig. 2 is a graph showing the experimental results of the relationship between the film formation conditions and optical characteristics of the phase shift layer of the phase shift mask. Fig. 3 is a process diagram for explaining a method of manufacturing a phase shift mask according to a second embodiment of the present invention. [Main component symbol description] 1 '2 phase shift mask 10 transparent substrate 11, 11P1, 11P2 light shielding layer 12 photoresist layer 12P1 ' 12P2 photoresist pattern 13, 13P1, 13P2 phase shift layer 14 photoresist layer 14P1 ' 14P2 light Resistance pattern 19/21