1329792 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種新穎的光阻顯影組成物； —種適合於使用在半導體裝置及液晶顯示器裝置 光阻顯影組成物’因爲其具有一好的抗腐蝕金屬 一好的抗腐蝕在基板上形成之不同金屬的層積層 及好的顯影性質。 【先前技術】 傳統上，半導體裝置及液晶顯示器裝置通常 影方法來製造’其包括在蝕刻處理或擴散處理之 對活化輻射（諸如紫外線、遠紫外線、準分子雷射 及電子束）敏感的光阻塗佈在一基板上，以選擇性 下面的基板；乾燥該光阻以形成一光阻層；選擇 光阻層曝露至活化輻射；及顯影該已曝光的光阻 該基板上形成一光阻圖案。 在該微影方法中，通常已使用一不含金屬離 鹼作爲主要組分之鹼性水溶液，以防止半導體裝 顯示器裝置的電性質損壞。 改良顯影性質的顯影液體已爲熟知，其可藉 添加劑加入至包含上述提及之有機鹼作爲主要組 液（例如，包含0 · 2至3 · 5重量％的氫氧化四甲基銨 10重量％的多羥基醇之水性顯影液體）而製備（日本 公開公報案號64- 1 9344) » 在半導體裝置及液晶顯示器裝置之製造中， 一 5 - 特別關於 之製造的 基板性、 之金屬性 已利用微 前，將一 、X-射線 地保護在 性地將該 層，以在 子的有機 置及液晶 由將一些 分的水溶 與0.2至 專利申請 具有金屬 1329792 層（諸如鋁層’用來形成電極電路）之矽晶圓或玻璃板會被 用來作爲基板。在該基板上的金屬層可利用微影方法進行 圖案化。但是’熟知的顯影液體會趨向於腐蝕該金屬層。 該最近受到注意的可作爲薄膜電晶體（TFT)顯示裝置之基板 通常包含一玻璃板、一在該玻璃板上的透明導電層（諸如氧 化銦層及氧化銦錫層（ITO層））及一在該導電層上以氣相沉 積之鋁層。在使用習知的顯影液體來微影具有不同金屬層 積層的此些基板之鋁層而圖形化中，可能會發生鋁層或接 觸該鋁層的另一種金屬之腐蝕。因此，對減低顯影液體的 腐蝕趨勢已有強烈的需求。 爲了解決上述問題，日本專利申請公開公報案號8-1 60634提出加入20至50重量％的多羥基醇至包含有機鹼 作爲主要組分的光阻顯影液體中。但是，所建議的顯影液 體雖然對金屬有較少的腐蝕，但其顯影性質差。換句話說， 所建議的顯影液體增加最少曝光而顯現出不足的顯影性 質，當與已被廣泛使用在技藝中之包含2.38重量％的氫氧 化四甲基銨之顯影液體來作比較時。 【發明內容】 考慮到技藝中的上述情況，本發明之目標爲提供一種 適合於使用在半導體裝置及液晶顯示裝置之製造的光阻顯 影組成物，因爲其具有金屬基板之優良的抗腐蝕性及優良 的顯影性質。 由於對發展金屬基板之具有優良的抗腐蝕性之光阻顯 影組成物之大量硏究結果，本案發明人已發現，藉由加入 -6- 1329792 特定量的糖化合物及多羥基醇至包含有機鹼作爲主要組分 之顯影液體中 '而製備的光阻顯影組成物，其同時具有優 良的抗腐蝕性及顯影性質。本發明係根據此硏究發現而達 成。 可使用在本發明之組成物中的有機鹼，可爲具有直 鏈、分枝或環狀結構之一級、二級或三級胺。其實例包括 二胺基烷類，諸如1,3-二胺基丙烷；芳基胺類，諸如4,4，_ 二胺基二苯基胺；烷基胺類，諸如N，N'·二胺基二烷基胺； 及具有形成3至5員環的碳原子和1或2個形成環的雜原 子（其可選自於氮原子、氧原子及硫原子）之雜環胺類，諸 如吡咯、吡咯烷、吡咯烷酮、吡啶、嗎福啉、吡畊、哌啶' 口惡唑及噻唑。此外，較低的烷基四級銨鹽亦可提供作爲 該有機鹼。其實例包括氫氧化四甲基銨、氫氧化四乙基銨、 氫氧化四丙基銨、氫氧化三甲基（2 -羥乙基）銨、氫氧化三乙 基（2-羥乙基）銨、氫氧化三丙基（2-羥乙基）銨及氫氧化三甲 基（1-羥乙基）銨。在上述的有機鹼當中，較佳爲較低的烷基 四級銨鹽類，特別佳爲氫氧化四甲基銨。這些有機鹽類可 單獨使用或二種或多種組合著使用。 可根據有機鹼型式及所欲使用的光阻型式以適合地選 擇該有機鹼的濃度，通常爲該光阻顯影組成物的I至10重 量％，較佳爲2至8重量％。若少於1重量％，則光阻無法 良好地顯影。若超過10重量％，光阻在非曝光區域的損失 會不利地增加，而難以形成精確的光阻圖案。 -7- 1329792 本發明之光阻顯影組成物可進一步包含一些添加劑， 諸如界面活性劑類、潤滑劑類、潤溼劑類、安定劑類及溶 解輔助劑類，其已通常已使用在習知的光阻顯影組成物中， 只要其不會使本發明之目標相反地無效。 藉由使用本發明之光阻顯影組成物，沉積在基板上的 金屬薄膜可被精確地圖案化而沒有腐蝕該金屬薄膜，因爲 其具有優良的腐蝕抑制效應。可有效地防止腐蝕之金屬薄 膜可包含鋁及鋁合金類，諸如鋁-銅合金類、鋁-矽合金類、 鋁·鈸合金類及鋁-锆合金類》本發明之光阻顯影組成物亦 可有效地防止具有不同金屬的層積層之基板腐鈾。例如， 其可有效地處理在包含銦及錫的氧化物透明導電層（諸如氧 化銦層及IT0層）上具有以氣相沉積鋁層之基板，而沒有造 成鋁層及ITO層腐蝕。 欲由本發明之光阻顯影組成物的光阻欲顯影可爲負型 式及正型式，且並不限制爲特別的型式，只要其可由熟知 的鹼性水溶液顯影。 隨著其優良的防止腐蝕效應，本發明之光阻顯影組成 物可有效地顯影塗佈在金屬層上之光阻而沒有造成金屬腐 蝕，且亦可有效地處理具有不同的金屬層積層之基板。因 此，該光阻顯影組成物特別適合於使用在需要具有精確的 電極電路之半導體裝置及液晶顯示器裝置的製造，及使用 具有不同的金屬層積層之基板的TFT顯示裝置之製造中。 【實施方式】 本發明將參考下列實例更詳細地解釋，其不應該解釋 -9- 1329792 爲本發明之範圍的限制。 管例1-3及比較例1-9 將包含玻璃板的基板（在該玻璃板上含有1 〇〇〇 A的ITO 層，且在該ITO層上含有3000 A的鋁層），於23 °c下浸入 編列在表1的每種組成物中6 0秒，以水沖洗且由氮吹乾。 在光學顯微鏡下觀察鋁-ITO層積層的表面，根據標定A(當 在表面上無觀察到腐蝕凹坑時）及標定B(當在表面上觀察到 腐蝕凹坑時）評估抗腐蝕性。結果顯示在表【° -10- 1329792 表】 有機鹼 (重量％) 糖化合物 (重量％) 多羥基醇 (重量％) 抗腐蝕性 實例 1 ΤΜΑΗ 木糖醇 1，2-丙二醇 A 3.0 6 6 2 ΤΜΑΗ 山梨糖醇 1，2-丙二醇 A 3.0 6 6 3 ΤΜΑΗ 木糖醇 1，3-丁二醇 A 3.0 6 6 比較例 1 ΤΜΑΗ - - B 2.38 2 ΤΜΑΗ - - B 3.0 3 ΤΜΑΗ 木糖醇 - A 3.0 6 4 ΤΜΑΗ 山梨糖醇 - A 3.0 6 5 ΤΜΑΗ - 1，2-丙二醇 B 3.0 6 6 ΤΜΑ Η - 1，3-丁二醇 B 3.0 6 7 ΤΜΑΗ - 甘油 A 3.5 20 8 ΤΜΑΗ - 乙二醇 A 4.0 30 9 ΤΜΑΗ - 1，2-丙二醇 40 A 3.5 ΤΜΑΗ :氫氧化四甲基銨 1329792 及卜卜.較例10·18 將一正型光阻塗佈在6吋砂晶圓上月 板上烘烤3分鐘，以形成一厚約1 7 000 A 不同強度曝光後，將該攜有光阻層的晶圓] 列在表2的每種組成物中6 0秒，以水沖洗 量曝光前後之光阻層厚度（利用由n&k有限 分析器1 2 8 0)，以測量顯影該光阻的最小曝 光區域的損失。結果顯示在表2。 在I 2 0 °C的加熱 的光阻層。在以 令23 °C下浸入編 及由氮吹乾。測 公司製造之n&k 光和光阻在非曝 -12- 1329792 表2 有機鹼 (重量％) 糖化合物 (重量％) 多羥基醇 (重量％) 顯影件質 最小曝光在非曝光區域 (毫焦耳） 的損失(A) 實例 4 TMAH 木糖醇 1,2-丙二醇 15 210 3.0 6 6 5 TMAH 山梨糖醇 1，2-丙二醇 16 195 3.0 6 6 6 TMAH 木糖醇 1，3-丙二醇 15 210 3.0 6 6 比較例 10 TMAH - - 15 200 2.38 11 TMAH - - 10 210 3.0 12 TMAH 木糖醇 45 5 3.0 6 13 TMAH 山梨糖醇6 - 55 5 3.0 14 TMAH - 1，2-丙二醇 8 400 3.0 6 15 TMAH - 1，3-丁二醇 8 390 3.0 6 16 TMAH - 甘油 30 10 3.5 20 17 TMAH - 乙二醇 25 20 4.0 30 18 TMAH - 1，2-丙二醇 40 >100 -100* 3.5 TMAH :氫氧化四甲基銨 1329792 *在比較例1 8中，該光阻在顯影處理期間膨脹而增加在非 曝光區域中的光阻層厚度。因此，損失由負値表示。 實例1 ·6的光阻顯影組成物顯示出改善的抗腐蝕性， 同時其顯影性質顯示出等於已廣泛使用在半導體裝置及液 晶顯示器裝置之製造中的那些顯影液體（比較例1及1 〇)。 比較例3 -4及7 -9的組成物不會腐蝕在鋁/ΙΤ〇薄層中的鋁 及ΙΤΟ，但是其不利地需要長的曝光時間（如可由比較例 12-13 及 16-18 明瞭）。 如上所述’有機鹼、糖化合物及多羥基醇之組合可提供一 適合於使用來製造半導體裝置及液晶顯示器裝置之光阻顯 · 影組成物’因爲其金屬基板具有好的抗腐餓性 '該好的抗 - 腐蝕在基板上形成之不同金屬層積層的金屬性及好的顯影 - 性質。 · -14-1329792 玖Invention Description: [Technical Field] The present invention relates to a novel photoresist development composition; a photoresist development composition suitable for use in a semiconductor device and a liquid crystal display device because it has a good Corrosion-resistant metal is a good corrosion-resistant layer of different metals formed on the substrate and good development properties. [Prior Art] Conventionally, semiconductor devices and liquid crystal display devices have generally been fabricated to produce 'resistances that are sensitive to activating radiation (such as ultraviolet rays, far ultraviolet rays, excimer lasers, and electron beams) including etching treatment or diffusion treatment. Coating on a substrate to select the underlying substrate; drying the photoresist to form a photoresist layer; selecting the photoresist layer to expose to the activating radiation; and developing the exposed photoresist to form a photoresist pattern on the substrate . In the lithography method, an alkaline aqueous solution containing no metal ion as a main component has been generally used to prevent electrical property damage of the semiconductor-mounted display device. A developing liquid having improved developing properties is well known, and it may be added as an additive to the organic liquid containing the above-mentioned organic base as a main group liquid (for example, 10% by weight to 0. 2 to 3.5% by weight of tetramethylammonium hydroxide). In the manufacture of a semiconductor device and a liquid crystal display device, in the manufacture of a semiconductor device and a liquid crystal display device, the substrate property and the metallity which have been manufactured in particular have been utilized. In the first place, the X-ray layer protects the layer in an organic manner and the liquid crystal is dissolved in water by a portion of 0.2 to a patent application having a layer of 1,329,792 (such as an aluminum layer) used to form an electrode. Circuits) wafers or glass sheets are used as substrates. The metal layer on the substrate can be patterned using a lithography method. However, the well-known developing liquid tends to corrode the metal layer. The recently noted substrate that can be used as a thin film transistor (TFT) display device generally comprises a glass plate, a transparent conductive layer (such as an indium oxide layer and an indium tin oxide layer (ITO layer)) on the glass plate, and a An aluminum layer is deposited on the conductive layer in a vapor phase. In the patterning of the aluminum layer of such substrates having different metal layers by conventional developing liquids, corrosion of the aluminum layer or another metal contacting the aluminum layer may occur. Therefore, there is a strong demand for reducing the corrosion tendency of the developing liquid. In order to solve the above problem, Japanese Patent Application Laid-Open No. 8-1 60634 proposes to add 20 to 50% by weight of a polyhydric alcohol to a photoresist developing liquid containing an organic base as a main component. However, the proposed developer liquid has poor development properties although it has less corrosion to metals. In other words, the proposed developing liquid increases the minimum exposure to exhibit insufficient developability when compared with a developing liquid which has been widely used in the art and contains 2.38 wt% of tetramethylammonium hydroxide. SUMMARY OF THE INVENTION In view of the above circumstances in the art, an object of the present invention is to provide a photoresist development composition suitable for use in the manufacture of a semiconductor device and a liquid crystal display device because it has excellent corrosion resistance of a metal substrate and Excellent development properties. The inventors of the present invention have found that by adding a specific amount of saccharide compound and polyhydric alcohol to -6- 1329792 to include an organic base, as a result of a large number of studies on the development of a photoresist composition having excellent corrosion resistance to a metal substrate. A photoresist developing composition prepared as a main component in a developing liquid, which has both excellent corrosion resistance and developing properties. The present invention has been achieved based on the findings of this study. The organic base in the composition of the present invention may be used, and may be a primary, secondary or tertiary amine having a linear, branched or cyclic structure. Examples thereof include diaminoalkanes such as 1,3-diaminopropane; arylamines such as 4,4,-diaminodiphenylamine; alkylamines such as N, N'. An aminodialkylamine; and a heterocyclic amine having a carbon atom forming a 3 to 5 membered ring and 1 or 2 ring-forming hetero atoms (which may be selected from a nitrogen atom, an oxygen atom and a sulfur atom), such as Pyrrole, pyrrolidine, pyrrolidone, pyridine, morphine, pyridin, piperidine's oxazole and thiazole. Further, a lower alkyl quaternary ammonium salt can also be provided as the organic base. Examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, and triethyl(2-hydroxyethyl) hydroxide. Ammonium, tripropyl (2-hydroxyethyl) ammonium hydroxide and trimethyl (1-hydroxyethyl) ammonium hydroxide. Among the above organic bases, preferred are lower alkyl quaternary ammonium salts, particularly preferably tetramethylammonium hydroxide. These organic salts may be used singly or in combination of two or more. The concentration of the organic base can be suitably selected depending on the type of the organic base and the type of photoresist to be used, and is usually from 1 to 10% by weight, preferably from 2 to 8% by weight, based on the resist development composition. If it is less than 1% by weight, the photoresist cannot be developed well. If it exceeds 10% by weight, the loss of the photoresist in the non-exposed area may be disadvantageously increased, and it is difficult to form an accurate photoresist pattern. -7- 1329792 The photoresist development composition of the present invention may further comprise additives such as surfactants, lubricants, wetting agents, stabilizers, and dissolution aids, which have generally been used in the prior art. The photoresist development composition is as long as it does not invalidate the object of the present invention. By using the photoresist development composition of the present invention, the metal thin film deposited on the substrate can be accurately patterned without etching the metal thin film because it has an excellent corrosion inhibiting effect. The metal film which can effectively prevent corrosion can include aluminum and aluminum alloys, such as aluminum-copper alloys, aluminum-bismuth alloys, aluminum-bismuth alloys, and aluminum-zirconium alloys. The photoresist development composition of the present invention is also The substrate uranium having a laminated layer of different metals can be effectively prevented. For example, it can effectively treat a substrate having a vapor-deposited aluminum layer on an oxide transparent conductive layer containing indium and tin (such as an indium oxide layer and an IT0 layer) without causing corrosion of the aluminum layer and the ITO layer. The photoresist to be developed by the photoresist development composition of the present invention may be of a negative type and a positive type, and is not limited to a specific type as long as it can be developed from a well-known alkaline aqueous solution. With its excellent corrosion prevention effect, the photoresist development composition of the present invention can effectively develop the photoresist coated on the metal layer without causing metal corrosion, and can also effectively process substrates having different metal laminate layers. . Therefore, the photoresist developing composition is particularly suitable for use in the manufacture of a semiconductor device and a liquid crystal display device which are required to have an accurate electrode circuit, and in the manufacture of a TFT display device using a substrate having a different metal layer. [Embodiment] The present invention will be explained in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention. Tube Example 1-3 and Comparative Example 1-9 A substrate comprising a glass plate (having an ITO layer of 1 Å on the glass plate and an aluminum layer of 3000 A on the ITO layer) at 23 ° C was immersed in each of the compositions listed in Table 1 for 60 seconds, rinsed with water and blown dry with nitrogen. The surface of the aluminum-ITO layer was observed under an optical microscope, and the corrosion resistance was evaluated according to the calibration A (when no corrosion pits were observed on the surface) and the calibration B (when corrosion pits were observed on the surface). The results are shown in the table [° -10- 1329792] Organic base (% by weight) Sugar compound (% by weight) Polyhydric alcohol (% by weight) Corrosion resistance Example 1 Xylitol 1,2-propanediol A 3.0 6 6 2 ΤΜΑΗ Sorbitol 1,2-propanediol A 3.0 6 6 3 ΤΜΑΗ Xylitol 1,3-butanediol A 3.0 6 6 Comparative Example 1 ΤΜΑΗ - - B 2.38 2 ΤΜΑΗ - - B 3.0 3 ΤΜΑΗ Xylitol-A 3.0 6 4 ΤΜΑΗ Sorbitol - A 3.0 6 5 ΤΜΑΗ - 1,2-propanediol B 3.0 6 6 ΤΜΑ Η - 1,3-butanediol B 3.0 6 7 ΤΜΑΗ - Glycerol A 3.5 20 8 ΤΜΑΗ - Ethylene glycol A 4.0 30 9 ΤΜΑΗ - 1,2-propanediol 40 A 3.5 ΤΜΑΗ : tetramethylammonium hydroxide 1329792 and ib. Comparative Example 10.18 A positive photoresist is coated on a 6-inch sand wafer. Bake for 3 minutes to form a thickness of about 1 7 000 A. After exposure to different intensities, the wafer carrying the photoresist layer is listed in each composition of Table 2 for 60 seconds, before and after exposure with water. Photoresist layer thickness (utilized by n&k finite analyzer 1 2 80) to measure The exposed photoresist minimum light loss region. The results are shown in Table 2. A heated photoresist layer at I 20 °C. Dip in at 23 °C and blow dry with nitrogen. Manufactured by n&k light and photoresist in non-exposed -12-1329792 Table 2 Organic base (% by weight) Sugar compound (% by weight) Polyhydric alcohol (% by weight) Development part Minimum exposure in non-exposed areas (milli-joules) Loss (A) Example 4 TMAH xylitol 1,2-propanediol 15 210 3.0 6 6 5 TMAH Sorbitol 1,2-propanediol 16 195 3.0 6 6 6 TMAH Xylitol 1,3-propanediol 15 210 3.0 6 6 Comparative Example 10 TMAH - - 15 200 2.38 11 TMAH - - 10 210 3.0 12 TMAH Xylitol 45 5 3.0 6 13 TMAH Sorbitol 6 - 55 5 3.0 14 TMAH - 1,2-propanediol 8 400 3.0 6 15 TMAH - 1,3-butanediol 8 390 3.0 6 16 TMAH - glycerol 30 10 3.5 20 17 TMAH - ethylene glycol 25 20 4.0 30 18 TMAH - 1,2-propanediol 40 > 100 -100* 3.5 TMAH : hydrogen Tetramethylammonium oxide 1329992 * In Comparative Example 18, the photoresist was expanded during the development treatment to increase the thickness of the photoresist layer in the non-exposed regions. Therefore, the loss is represented by negative 値. The photoresist developing composition of Example 1 showed improved corrosion resistance while its developing properties showed those developing liquids which were widely used in the manufacture of semiconductor devices and liquid crystal display devices (Comparative Examples 1 and 1). . The compositions of Comparative Examples 3 - 4 and 7 - 9 did not corrode aluminum and tantalum in the aluminum/tantalum layer, but it disadvantageously required a long exposure time (as can be seen by Comparative Examples 12-13 and 16-18). ). As described above, the combination of an organic base, a sugar compound and a polyhydric alcohol can provide a photoresist display composition suitable for use in the manufacture of a semiconductor device and a liquid crystal display device because its metal substrate has good resistance to hunger. The good anti-corrosion metallity and good development-properties of different metal layer layers formed on the substrate. · -14-