1285915 14500twf.doc/g 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種半導體製程，且特別是有關於一 種光阻層的表面處理方法以及使用前述表面處理方法以形 成圖案化光阻層的方法。 ^ 【先前技術】 • 在要求電路積集化越來越高的情況下，整個電路元件 φ 大小的設計也被迫往尺寸不停縮小的方向前進，目前半導 體製私已經進入90奈米製程。而整個半導體製程中最舉足 輕重的可說是微影㈣伽她嗯叩㈣製程，任何關鍵尺寸 的決定，都是由微影這個步驟來主導的。 ;、、i而，於被影製程中，藉由對光阻層進行曝光及顯影 步驟以形成的圖案化光阻層，在線寬尺寸縮小的要求下， 圖案化光阻層的寬度相對變窄而使得光阻層輪廓 =易維持，甚至發生倒塌(c〇llapse)的問題。其次，微影線 寬尺寸縮小及光阻成分因素也會導致蝕刻時，光阻不耐蝕 刻電漿之高溫，而造成光阻倒塌。 圖1為在90奈米製程中，利用習知之微影製程所得 之圖案化光阻層的照片圖。由圖1可知，圖案化光阻層由 於f度相對變窄而使其輪廓出現扭曲的現象，如此將使得 後縯在以此光阻層作為罩幕而進行蝕刻製程時，欲蝕刻之 膜層產生圖案失真或是導致解析度降低的問題。 【發明内容】 本毛明的目的就是在提供一種光阻層的表面處理方 5 1285915 14500twf.doc/g t見ί有效轉光闕案，避歧行_轉㈣產生失真 方法的是提供—種圖案化光阻層的形成 $成輪廓較為精確之圖案化光阻 係在一 开出:種光阻層的表面處理方二此處理方法 +日日形成一圖案化之光阻層後，使用至少含一溴 化虱或峨化氫之反應氣體對光阻層進行一表面處^驟，、 面形成-硬化層(心 f理步驟係與钱刻製程於同位(in-situ)進行。 一材料H提化光阻層的形成方法，其係先於 上开!H成:底層抗反射層。接著，於底層抗反射層 化脅之及光阻層。然後’使用至少含一溴化氫或碳 乳體對圖案化光阻層進行一表面處理步驟，以 與钱刻製程於同位進行。 ，、巾表面處理步驟係 於-= 月L提Γ?圖案化光阻層的形成方法，其係先 底層抗反射層。接著，於底層抗反射 阻層。然後’以圖案化光阻層為罩幕 對^層抗反射層進行一钱刻製程。之後，使用至少含 =或:=之反應氣體對圖案化光阻層進行-表面處理 二〖〈於圖案化光阻層表面形成一硬化層，其中表 面處理步驟係與蝕刻製程於同位進行。 /、 依照本發明的另-較佳實施例，上述之圖案化 的形成方法，更包括在形成底層抗反射層之前，於材料^ 1285915 1450〇twf.doc/g 上形成一罩幕層，其中罩幕層之材質包括 餘刻選擇性的材料，其例如是介電材料，而此;電 如是氮化矽或氧化矽。 ％材枓例 /依照本發明的另-較佳實施例，上述之_化 的形成方法’其巾材料層之㈣例如是多晶㈣氮化曰 依照本發明的另一較佳實施例，在上述之圖 f的形成方法或絲層的表面處理方法巾，反應氣= 量例如是3 G〜5GGs_，此反應氣體所產&電^ 如是500伏特以下。另外，.而^之冤水其電壓例 ;a 9 表面處里^^驟所使用之溫度例 士疋 〇 C，所使用之壓力例如是5〜80mT〇rr。 依照本發明的另一較佳實施例，在上述之圖案化 層的形成方法或光阻層的表面處理方法巾，圖案化光阻芦 =材吳包括深紫外光光阻材料，其例如是丨57麵光阻二 料、193mn光阻材料、248nm光阻材料或i57nm以 阻材料。 ^ 由於本龟明在钱刻製程之前，係先對欲作為姓刻罩幕 之圖案化光阻層進行表面處理步驟而使其表面產生硬化 層，因此可以有效維持圖案化之光阻層的輪廓，進而避免 =化光㈣產生變形甚至於倒塌的現象。所以，利用本 毛月之方法可以減少在後續蝕刻製程中，欲蝕刻之膜層產 生圖案失真的問題。 ▲為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細 明如下。 1285915 1450〇twfdoc/g 【實施方式】 由於藉由微影製程所得之圖案化之光阻層，在線寬越 來越的情況下，容易產生變形或是倒塌的問題，因此本發 明係提出一種光阻層的表面處理方法來處理上述之問題。 此光阻層的表面處理方法是在利用微影設備在晶圓上形成 一圖案化之光阻層之後，將此晶圓移至蝕刻反應中，使用 至少含溴化氫或碘化氫之反應氣體，對光阻層進行一表面 處理步驟，以在光阻層表面形成一硬化層。 其中上述之表面處理步驟是利用射頻電壓將反應氣 體激發為電漿，以在光阻層表面形成硬化層，而此硬化層 將可有效維持圖案化光阻層之輪廓。另外，上述之光阻^ 的材質例如是深紫外光(Deep uv)光阻材料，如157nm ^ 阻材料、193nm光阻材料或248nm光阻材料。特別是，此 深紫外光光阻材料更可以是157nm以下之光阻材料，而這 些157mn以下之材料將可用於線寬小於45nm之製程中。° 此外，反應氣體的流量例如是3〇〜5〇〇sccm，較佳的流量是 lOOsccm，而此反應氣體所產生之電漿其電壓例如是$㈨ 伏特以下。另外，表面處理步驟所使用之溫度例如是2〇〜8〇 C，較佳的溫度是30。c，而使用之壓力例如是 5〜80mTorr，較佳的壓力是5mT〇rr。 另一方面，由於此表面處理步驟係蝕刻反應室中進 行，因此本發明之表面處理步驟係與蝕刻製程於同位中進 行。也就是說，在進行完本發明之表面處理步驟之後，即 可於同一反應室中，利用此具有硬化層之圖案化的光阻層 8 1285915 14500twf.doc/g 作為罩幕，繼續進行蝕刻製程。 在90奈米製程中，利用本 光阻層的照片圖係如圖2所示。+艾方法所得之圖案化 知，在圖1中，未使用本發明之^時參照圖1及圖2可 層出現扭曲變形的現象，而在圖2中，行表面處理的光阻 發明之表面處理後的光阻層，其 ^以明顯的看出經本 地維持。 ” “的圖案可相當完整 依照上述實施例所述之光阻； 可在光阻表面形成一硬化層，因此可‘ 二= :現:此可防止光阻層扭曲變形，甚至於 ，將詳述於下列實 圖3A〜圖3C為本發明一較佳實施例之 剖面圖。縣«3Α，首先提供—轉縣底細，= 半導體基底300上形成一墊氧化層31()，其材質例如是氧 化矽，形成的方法例如是熱氧化法。接著，在墊氧化層3ι〇 上形成一材料層320，其材質例如是氮化矽，形成的^ 例如是化學氣相沉積法。 然後，請繼續參照圖3A，在材料層32〇上形成一底 層抗反射層330，其形成方法例如是化學氣相沉積法。在 一較佳實施例中，於形成底層抗反射層33〇之前，更可在 材料層320上形成一罩幕層（未繪示）。 接下來，在底層抗反射層330上形成一圖案化光阻層 1285915 14500twf.doc/g 340,形成的方法例如是進行—微影製程。其中，圖案 .阻層340讀質例如是深紫外光(Deep UV)光阻材料，= 157nm光阻材料、193nm光阻材料或248·光阻材 特別是’ ^深紫外光触材料更可以是157nm以下之光阻 材料’而些157nm以下之材料將可用於線寬小於45_ * 之製程中。 •接著，使用至少含-填化氫或峨化氫之反應氣體對圖 _ #化光阻層340進行-表面處理步驟。此表面處理步驟例 如是以射頻電壓將反應氣體激發成電漿，此電裝將與圖案 化光阻層340進行反應，以在圖案化光阻層表面开》成 -硬化層35G，如此可以加強圖案化光阻層34()之結構。 其中，反應氣體的流量例如{3〇〜5〇〇sccm，較佳的流量是 lOOsccm。此外，反應氣體所產生之電漿其電壓例如是刈〇 伏特以下。另外’表面處理步驟所使用之溫度例如是％〜⑽ C，較佳的溫度是3〇。c，而使用之壓力例如是 5〜8〇mT0rr，較佳的壓力是5mT〇rr。其中，其中表面處理 ’步驟係與|虫刻製程同位進行。 除此之外，在一較佳實施例中，在上述之表面處理步 - 驟之後’更可以進行一光阻圖案縮小步驟(trim卿），以縮 小光阻圖案的尺寸。而在另一較佳實施例中，此光阻圖案 縮小步驟Φ可在®案化光阻層34〇進行表面處理步驟之前 進行。 接著，請參照圖3Β，以圖案化光阻層340為罩幕， 移除部份底層抗反射層330,以形成圖案化之底層抗反射1285915 14500twf.doc/g IX. Description of the Invention: [Technical Field] The present invention relates to a semiconductor process, and more particularly to a surface treatment method for a photoresist layer and using the foregoing surface treatment method to form a pattern The method of the photoresist layer. ^ [Prior Art] • In the case where the circuit integration is required to be higher and higher, the design of the entire circuit component φ size is forced to continue to shrink in size. Currently, the semi-conductor system has entered the 90 nm process. The most important thing in the entire semiconductor manufacturing process is the lithography (4) gamma 叩 四 (4) process, the decision of any key size is dominated by the lithography step. ;, i, in the shadowing process, by the exposure and development steps of the photoresist layer to form a patterned photoresist layer, the width of the patterned photoresist layer is relatively narrow, the width of the patterned photoresist layer is relatively narrow Therefore, the profile of the photoresist layer is easy to maintain, and even collapses. Secondly, the lithographic line width reduction and the photoresist component factor also cause the photoresist to resist the high temperature of the plasma during etching, which causes the photoresist to collapse. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photographic view of a patterned photoresist layer obtained by a conventional lithography process in a 90 nm process. It can be seen from FIG. 1 that the patterned photoresist layer is distorted due to the relatively narrowing of the f-degree, so that the film layer to be etched is performed after the etching process is performed using the photoresist layer as a mask. Pattern distortion or a problem that causes a decrease in resolution. SUMMARY OF THE INVENTION The purpose of the present invention is to provide a surface treatment of the photoresist layer 5 1285915 14500twf.doc / gt see ί effective conversion case, avoiding the _ turn (four) to produce distortion method is to provide a pattern The formation of the photoresist layer is more precise. The patterned photoresist is in the open state: the surface treatment of the photoresist layer. The processing method + the formation of a patterned photoresist layer on a daily basis, the use of at least The reaction gas of cesium bromide or hydrogen halide is subjected to a surface treatment of the photoresist layer, and the surface is formed into a hardened layer (the core step is performed in-situ with the engraving process). The method for forming the photoresist layer is preceded by the upper layer: H: the underlying anti-reflective layer. Then, the anti-reflective layer is applied to the photoresist layer and then the photoresist layer is used. Then 'at least one hydrogen bromide or carbon is used. The surface of the patterned photoresist layer is subjected to a surface treatment step in parallel with the engraving process. The surface treatment step of the towel is performed on the method of forming a patterned photoresist layer. The underlying anti-reflective layer. Next, the underlying anti-reflective layer. Then 'patterned The resist layer is a masking process for the anti-reflective layer of the layer. Thereafter, the patterned photoresist layer is subjected to surface treatment using a reaction gas containing at least = or := (in the surface formation of the patterned photoresist layer) a hardened layer, wherein the surface treatment step is performed in-situ with the etching process. /, According to another preferred embodiment of the present invention, the patterning forming method described above further comprises: before forming the underlying anti-reflective layer, in the material ^ A mask layer is formed on 1285915 1450〇twf.doc/g, wherein the material of the mask layer comprises a material of selective selectivity, which is, for example, a dielectric material, and the electric material is tantalum nitride or tantalum oxide. Illustrative/in accordance with another preferred embodiment of the present invention, the above-described method for forming a smear, wherein (4) of the material layer of the towel material is, for example, polycrystalline (tetra) cerium nitride according to another preferred embodiment of the present invention, The forming method of Fig. f or the surface treatment method of the silk layer, the reaction gas = amount is, for example, 3 G to 5 GGs_, and the reaction gas is produced at a voltage of 500 volts or less. ;a 9 Temperature example used in the surface疋〇C, the pressure used is, for example, 5 to 80 mT rr. According to another preferred embodiment of the present invention, the method of forming the patterned layer or the surface treatment method of the photoresist layer, patterned photoresist Lu = material Wu includes deep ultraviolet light photoresist material, which is, for example, 丨57 surface resist material, 193mn photoresist material, 248nm photoresist material or i57nm resist material. ^Because this turtle is in the process of the engraving process, Firstly, the surface of the patterned photoresist layer to be masked as a surname is subjected to a surface treatment step to form a hardened layer on the surface, so that the contour of the patterned photoresist layer can be effectively maintained, thereby avoiding deformation or even collapse of the light (4). Therefore, the method of the present month can reduce the problem of pattern distortion of the film layer to be etched in the subsequent etching process. The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. 1285915 1450〇twfdoc/g [Embodiment] Since the patterned photoresist layer obtained by the lithography process has a problem that deformation or collapse is likely to occur when the line width is more and more, the present invention proposes a light. The surface treatment of the resist layer handles the above problems. The surface treatment method of the photoresist layer is to use a lithography device to form a patterned photoresist layer on the wafer, and then move the wafer to an etching reaction using a reaction containing at least hydrogen bromide or hydrogen iodide. The gas is subjected to a surface treatment step of the photoresist layer to form a hardened layer on the surface of the photoresist layer. The surface treatment step described above is to excite the reaction gas into a plasma by using a radio frequency voltage to form a hardened layer on the surface of the photoresist layer, and the hardened layer can effectively maintain the contour of the patterned photoresist layer. In addition, the material of the above photoresist is, for example, a deep uv photoresist material, such as a 157 nm resist material, a 193 nm photoresist material, or a 248 nm photoresist material. In particular, the deep ultraviolet photoresist material can be a photoresist material of 157 nm or less, and these materials of 157 nm or less can be used in a process with a line width of less than 45 nm. Further, the flow rate of the reaction gas is, for example, 3 〇 to 5 〇〇 sccm, and the preferred flow rate is 100 sec, and the voltage of the plasma generated by the reaction gas is, for example, less than (9) volts. Further, the temperature used for the surface treatment step is, for example, 2 Torr to 8 Torr C, and a preferred temperature is 30. c, and the pressure used is, for example, 5 to 80 mTorr, and the preferred pressure is 5 mT 〇 rr. On the other hand, since the surface treatment step is performed in the etching reaction chamber, the surface treatment step of the present invention is carried out in the same manner as the etching process. That is to say, after the surface treatment step of the present invention is completed, the etching process can be continued in the same reaction chamber by using the patterned photoresist layer 8 1285915 14500 twf.doc/g having a hardened layer as a mask. . In the 90 nm process, the photo map using the photoresist layer is shown in Fig. 2. + The pattern obtained by the method of Ai, in Fig. 1, the phenomenon of distortion occurs in layers by referring to Figs. 1 and 2 without using the present invention, and in Fig. 2, the surface of the photoresist surface treated by the surface treatment After the treatment, the photoresist layer is clearly maintained locally. "The pattern can be quite complete in accordance with the photoresist described in the above embodiments; a hardened layer can be formed on the surface of the photoresist, so that it can be 'two =: now: this can prevent the photoresist layer from being distorted, or even 3A to 3C are cross-sectional views showing a preferred embodiment of the present invention. The county «3Α, first provided - the bottom of the county, = a pad oxide layer 31 () formed on the semiconductor substrate 300, the material of which is, for example, cerium oxide, formed by a thermal oxidation method. Next, a material layer 320 is formed on the pad oxide layer 3 ι, and the material thereof is, for example, tantalum nitride, and is formed, for example, by chemical vapor deposition. Then, referring to Fig. 3A, a bottom anti-reflective layer 330 is formed on the material layer 32, for example, by chemical vapor deposition. In a preferred embodiment, a mask layer (not shown) may be formed on the material layer 320 before the underlying anti-reflective layer 33 is formed. Next, a patterned photoresist layer 1285915 14500 twf.doc/g 340 is formed on the underlying anti-reflective layer 330, for example, by performing a lithography process. Wherein, the patterning layer 340 reading quality is, for example, a deep ultraviolet (Theep UV) photoresist material, = 157 nm photoresist material, 193 nm photoresist material or 248. Photoresist material, especially '^ deep ultraviolet light touch material can be Materials of photoresist below 157 nm' and materials below 157 nm will be used in processes with line widths less than 45 mm. • Next, a surface treatment step is performed on the photoresist layer 340 using a reaction gas containing at least hydrogen-filled or hydrogen halide. The surface treatment step is, for example, exciting the reaction gas into a plasma by a radio frequency voltage, and the electric device will react with the patterned photoresist layer 340 to open the surface-hardened layer 35G on the surface of the patterned photoresist layer. The structure of the patterned photoresist layer 34(). Here, the flow rate of the reaction gas is, for example, {3 〇 to 5 〇〇 sccm, and the preferred flow rate is 100 sec. Further, the plasma generated by the reaction gas has a voltage of, for example, 刈〇 volt or less. Further, the temperature used in the surface treatment step is, for example, % to (10) C, and the preferred temperature is 3 Torr. c, and the pressure used is, for example, 5 to 8 〇 mT0rr, and the preferred pressure is 5 mT 〇 rr. Among them, the surface treatment step is performed in the same position as the | In addition, in a preferred embodiment, a photoresist pattern reduction step can be performed after the surface treatment step described above to reduce the size of the photoresist pattern. In yet another preferred embodiment, the photoresist pattern reduction step Φ can be performed prior to the surface treatment step of the photoresist layer 34. Next, referring to FIG. 3A, the patterned photoresist layer 340 is used as a mask to remove a portion of the underlying anti-reflective layer 330 to form a patterned underlying anti-reflection layer.
1285915 14500twf.doc/g ，移除的方法例如是進行—_製程。之後， 案化光阻層340及底層抗反射層33〇& 圖 :層似，移除的方法例如是對材料層32。進行== 方參照圖^’移除_匕光阻層移除的 方务例如疋進行-#刻製程。再來，移除底層抗反身^ 0a’移除的方法例如是進行—糊製程 ^ 層320為罩幕，移除部份半導體基底· ’以 中形成溝渠，移除財法例如是進行_爛; 接下來，在形成溝渠360之後，可於溝渠36〇 介電材料以形成隔離結構’或是於溝渠遍中進料他 ^適^程。關於這個部分，使用者可依不同之需求進行合 I之4而5彡些製程為熟習此技術領域者所週知，在此 不再費述。 此外，在另一較佳實施例中，圖案化光阻層34〇形成 之後係可先以此®案化光阻層34〇為罩幕對底層抗反射層 進行姓刻，之後再對_化光阻層進行表面處理步驟，以 於圖案化光阻層表面，甚至於底層抗反射層表面形成一硬 化層，以有效維持圖案化光阻層之輪廓。 圖4A〜圖4C A本發明又一較佳實施例之間極製造流 程剖面圖。請參照® 4A ’首先提供一半導體基底4〇〇，並 於半導體基底_上形成—閘氧化層指，其材質例如是 氧化矽，形成的方法例如是熱氧化法。接著，在閘氧化層 111285915 14500twf.doc / g, the method of removal is for example - the process. Thereafter, the patterned photoresist layer 340 and the underlying anti-reflective layer 33 are similar to the layer, and the method of removal is, for example, the material layer 32. Perform the == square reference picture ^' remove _ 匕 photoresist layer removal, such as 疋 - -# 刻 process. Further, the method of removing the underlying anti-reflexive ^ 0a' removal is performed, for example, by performing a paste process layer 320 as a mask, removing a portion of the semiconductor substrate, and forming a trench therein, and removing the financial method, for example, is performed. Next, after the trench 360 is formed, the dielectric material may be formed in the trench 36 to form an isolation structure or to feed the trench in the trench. With regard to this part, the user can perform the combination of 4 according to different needs. 5 These processes are well known to those skilled in the art and will not be described here. In addition, in another preferred embodiment, after the patterned photoresist layer 34 is formed, the photoresist layer 34 can be used as a mask to mark the bottom anti-reflective layer, and then The photoresist layer is subjected to a surface treatment step to form a hardened layer on the surface of the patterned photoresist layer or even on the surface of the underlying anti-reflective layer to effectively maintain the contour of the patterned photoresist layer. 4A to 4C are cross-sectional views showing a process of manufacturing a pole between still another preferred embodiment of the present invention. Referring to Fig. 4A', a semiconductor substrate 4 is first provided, and a gate oxide layer is formed on the semiconductor substrate, and the material thereof is, for example, ruthenium oxide, and the formation method is, for example, thermal oxidation. Next, in the gate oxide layer 11
1285915 14500twf.doc/g ^捕層物’其材_或是其他可 幕ί目4Α，在材料層420上形成一罩 一較佳實二：:：= 成罩幕層430。之德，在置墓ά A on 展細罩幕層0上形成一底層抗反射 € 4〇，/、形成方法例如是化學氣相沉積法。 接下來，在底層抗反射層440上形成一圖案化光阻層 ，形成的方法例如是進行一微影製程。其中，圖案化光 阻層45〇之材貝例如是深紫外光(Deep UV)光阻材料，如 157=光阻材料、193麵光阻材料或248腿光阻材料等。 特別是，此深紫外光光阻材料更可以是157nm以下之光阻 這些157nm以下之材料將可用於線寬小於45· 接著，請參照圖4B，以圖案化光阻層45()為罩幕， 移除部份底層抗反射層440,⑽成醜化之底層抗反射 層440a，移除的方法例如是進行一蝕刻製程。 然後，使用至少含一溴化氫或碘化氫之反應氣體對圖 案，光阻層450進行一表面處理步驟。此表面處理步驟例 如是以射頻電壓將反應氣體激發成電漿，此電漿將與圖案 化光阻層450進行反應，以至少在圖案化光阻層45〇表面 形成一硬化層46〇，如此可以加強圖案化光阻層45〇之結 構其中’反應氣體的流量例如是3〇〜5〇〇sccrn，較佳的流 12 1285915 14500twf.doc/g θ 9Λ如。…另外表面處理步驟所使用之溫度例如 :的溫度是3〇。C，*使用之壓力例如是 牛赞：:U土的壓力是5mT°rr。其中’其中表面處理 步驟係與蝕刻製程同位進行。 除此之外，在一較佳實施例中 驟之後，更包括進行一光阻圖宰if4之表面處理步 小光阻圖案的尺寸步驟(―)，以縮 光阻# 450 η ★ Μ圖案、％小步驟係可在圖案化 二—〇進仃表面處理步驟之前或是之後進行。 層抗反= 二=:二圖案化光阻層45〇 μ 法例如是妨-Zfi，歸赌轉層㈣，移除的方 的方=是化光阻層彻’移除 層二=:f進行，程。然後， 對材料層420 H 例如是以罩幕層為罩幕， 接；办4丁一飯刻製程’以形成一閘極470。 形成源極：汲極形470之後’可於基底300中繼續 成r之元件。關於這個部分，使用二 域者所週知，=適之製程’而該些製程為熟習此技術領 咫知，在此不再贅述。 前，3圖5==中:在/層抗反射層進行钱刻 |層進仃表面處理步驟，以於圖案化光 1285915 14500twf.doc/g 阻層表面形成一硬化層 點:綜上所述’在本發明 的現象，以正確的進行圖案的轉移:生扭曲㈣或是倒塌 光阻提化光阻層進行^ 成更小的線寬 細效先阻圖案的尺寸，有助於達 然本發明已以較佳實施觸露如上U並非用以 =㉟明’任㈣習此技藝者，在不脫離本發明之精神 當可作些許之更動與潤飾，因此本發明之保護 乾圍㊆視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1為在90奈米製程中，利用習知之微影製程所得 之圖案化光阻層的照片圖。 圖2為在90奈米製程中，利用本發明之方法所得之 圖案化光阻層的照片圖。 圖3A〜圖3C為本發明另一較佳實施例之溝渠製造流 程剖面圖。 圖4A〜圖4C為本發明又一較佳實施例之閘極製造流 程剖面圖。 【主要元件符號說明】 300、4〇〇 :半導體基底 14 1285915 14500twf.doc/g 310 :墊氧化層 320、420 :材料層 330、440 :底層抗反射層 340、450 :圖案化光阻層 350、460 :硬化層 360 :溝渠 410 :閘氧化層 430 :罩幕層 470 :閘極 151285915 14500 twf.doc / g ^layers _ or other viscous elements, forming a cover on the material layer 420, a better two::: = mask layer 430. In the case of the tomb, A on the thin mask layer 0, a bottom anti-reflection is formed, and the formation method is, for example, chemical vapor deposition. Next, a patterned photoresist layer is formed on the underlying anti-reflective layer 440, for example, by performing a lithography process. The material of the patterned photoresist layer 45 is, for example, a deep ultraviolet photoresist material such as 157=photoresist material, 193 surface resist material or 248 leg photoresist material. In particular, the deep ultraviolet photoresist material may be a photoresist of 157 nm or less. These materials of 157 nm or less may be used for a line width of less than 45. Next, please refer to FIG. 4B to pattern the photoresist layer 45 () as a mask. A portion of the underlying anti-reflective layer 440 is removed, and (10) is etched into the underlying anti-reflective layer 440a. The removal is performed, for example, by an etching process. Then, the pattern, the photoresist layer 450 is subjected to a surface treatment step using a reaction gas containing at least hydrogen bromide or hydrogen iodide. The surface treatment step is, for example, exciting the reaction gas into a plasma by a radio frequency voltage, and the plasma will react with the patterned photoresist layer 450 to form a hardened layer 46 at least on the surface of the patterned photoresist layer 45. The structure of the patterned photoresist layer 45 can be enhanced, wherein the flow rate of the reaction gas is, for example, 3 〇 5 〇〇 sccrn, and the preferred flow 12 1285915 14500 twf. doc / g θ 9 . ...the temperature used for the surface treatment step, for example: the temperature is 3 Torr. C, * The pressure used is, for example, Niuzan:: The pressure of U soil is 5mT °rr. Wherein the surface treatment step is performed in the same manner as the etching process. In addition, after a step in a preferred embodiment, the step of performing a size step (-) of performing a photo-resistance step on the small photoresist pattern of the if4 is performed to reduce the light-resistance pattern. The % small step can be performed before or after the patterning process. Layer anti-reverse = two =: two patterned photoresist layer 45 〇 μ method for example, it is -Zfi, gambling layer (four), the square of the removed side = is the photoresist layer to remove the layer two =: f Carry out, Cheng. Then, the material layer 420 H is, for example, covered by a mask layer, and then formed into a gate 470. Forming the source: the drain 470 is followed by the element that can continue to be r in the substrate 300. With regard to this part, it is well known to those skilled in the art that the process is known to those skilled in the art and will not be described here. Before, 3, Fig. 5 == middle: in the / layer anti-reflective layer, the surface layering process is performed to form a hardened layer on the surface of the patterned layer 1285915 14500 twf.doc/g: 'In the phenomenon of the present invention, the pattern is transferred correctly: the raw twist (four) or the collapsed photoresist is used to carry out the photoresist layer to make the smaller line width fine-grained first-resistance pattern size, which helps the Daren The invention has been described with a preferred embodiment as described above. U is not intended to be used by those skilled in the art, and may be modified and retouched without departing from the spirit of the invention. The scope defined in the patent application is subject to change. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photographic view of a patterned photoresist layer obtained by a conventional lithography process in a 90 nm process. Figure 2 is a photographic representation of a patterned photoresist layer obtained by the method of the present invention in a 90 nm process. 3A to 3C are cross-sectional views showing a manufacturing process of a ditch according to another preferred embodiment of the present invention. 4A to 4C are cross-sectional views showing a gate manufacturing process according to still another preferred embodiment of the present invention. [Main component symbol description] 300, 4: semiconductor substrate 14 1285915 14500twf.doc / g 310: pad oxide layer 320, 420: material layer 330, 440: bottom anti-reflection layer 340, 450: patterned photoresist layer 350 460: hardened layer 360: trench 410: gate oxide layer 430: mask layer 470: gate 15