JP4451172B2 - Photoresist composition for liquid crystal display device circuit - Google Patents
Photoresist composition for liquid crystal display device circuit Download PDFInfo
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- JP4451172B2 JP4451172B2 JP2004070773A JP2004070773A JP4451172B2 JP 4451172 B2 JP4451172 B2 JP 4451172B2 JP 2004070773 A JP2004070773 A JP 2004070773A JP 2004070773 A JP2004070773 A JP 2004070773A JP 4451172 B2 JP4451172 B2 JP 4451172B2
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- display device
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- 229920002120 photoresistant polymer Polymers 0.000 title claims description 93
- 239000000203 mixture Substances 0.000 title claims description 68
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 55
- 229920005989 resin Polymers 0.000 claims description 25
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- 150000001875 compounds Chemical class 0.000 claims description 23
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- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 13
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 11
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
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- 229920003002 synthetic resin Polymers 0.000 claims description 9
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 8
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- 238000004528 spin coating Methods 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- VWRUXXHWUZUAMT-UHFFFAOYSA-N C1=CC(O)(O)C(O)C(O)=C1C(=O)C1=CC=CC=C1 Chemical compound C1=CC(O)(O)C(O)C(O)=C1C(=O)C1=CC=CC=C1 VWRUXXHWUZUAMT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ALVGSDOIXRPZFH-UHFFFAOYSA-N [(1-diazonioimino-3,4-dioxonaphthalen-2-ylidene)hydrazinylidene]azanide Chemical compound C1=CC=C2C(=N[N+]#N)C(=NN=[N-])C(=O)C(=O)C2=C1 ALVGSDOIXRPZFH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
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- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007687 exposure technique Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B11/00—Buckles; Similar fasteners for interconnecting straps or the like, e.g. for safety belts
- A44B11/20—Buckles; Similar fasteners for interconnecting straps or the like, e.g. for safety belts engaging holes or the like in strap
- A44B11/24—Buckle with movable prong
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B11/00—Buckles; Similar fasteners for interconnecting straps or the like, e.g. for safety belts
- A44B11/001—Ornamental buckles
Landscapes
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Liquid Crystal (AREA)
Description
本発明は液晶表示装置回路、半導体集積回路などの微細回路の製造に用いられる液晶表示装置回路用フォトレジスト組成物に関し、さらに詳しくは1度の露光、現像工程で2乃至3回の露光、現像工程進行効果を得るのに有効な液晶表示装置回路用フォトレジスト組成物に関する。 The present invention relates to a photoresist composition for a liquid crystal display device circuit used for the production of a fine circuit such as a liquid crystal display device circuit and a semiconductor integrated circuit, and more particularly, exposure and development two to three times in one exposure and development process. The present invention relates to a photoresist composition for a liquid crystal display device circuit which is effective for obtaining a process progress effect.
液晶表示装置回路または半導体集積回路のように微細な回路パターンは基板上に形成された絶縁膜または導電性金属膜に液晶表示装置回路用フォトレジスト組成物を均一にコーティングまたは塗布し、所定の形状のマスク存在下でコーティングされた液晶表示装置回路用フォトレジスト組成物を露光して現像し、目的とする形状のパターンを作る。その後、パターンが形成されたフォトレジスト膜をマスクとして用いて金属膜または絶縁膜をエッチングし、残存するフォトレジスト膜を除去して基板上に微細回路を形成する。このような液晶表示装置回路用フォトレジスト組成物は、露光される部分の溶解度変化によってネガティブ型とポジティブ型に分類される。 A fine circuit pattern such as a liquid crystal display device circuit or a semiconductor integrated circuit is obtained by uniformly coating or applying a photoresist composition for a liquid crystal display device circuit on an insulating film or a conductive metal film formed on a substrate, and having a predetermined shape. The photoresist composition for a liquid crystal display device circuit coated in the presence of a mask is exposed and developed to form a pattern having a desired shape. Thereafter, the metal film or the insulating film is etched using the patterned photoresist film as a mask, and the remaining photoresist film is removed to form a fine circuit on the substrate. Such a photoresist composition for a liquid crystal display device circuit is classified into a negative type and a positive type depending on the solubility change of the exposed portion.
実用的な面で重要な液晶表示装置回路用フォトレジスト組成物の特性は、形成されたレジスト膜の感光速度、現像コントラスト、解像度、基板との接着力、残膜率、回路線幅均一度(CD uniformity)及び人体安全性などの使用便宜性を含む。 The characteristics of the photoresist composition for liquid crystal display device circuits, which are important in practical aspects, are the resist speed of the formed resist film, the development contrast, the resolution, the adhesion to the substrate, the remaining film ratio, and the circuit line width uniformity ( CD uniformity) and convenience of use such as human safety.
特に、1回の露光、現像工程で2回以上の露光、現像工程進行効果を得るのに有効なフォトレジスト組成物の特性は半露光部の残膜均一度(Remain Film Thickness uniformity)である。 In particular, the characteristic of the photoresist composition effective for obtaining the effect of progressing the exposure process and development process twice or more in one exposure and development process is the residual film thickness uniformity of the half-exposed part.
現在液晶表示装置回路には主にTFTが用いられる。このようなTFT回路は液晶表示装置回路用フォトレジスト組成物を均一にコーティングまたは塗布し、所定の形状のマスク存在下でコーティングされた液晶表示装置回路用フォトレジスト組成物を露光して現像し、目的とする形状のパターンを作った後、パターンが形成されたフォトレジスト膜をマスクとして用いて金属膜または絶縁膜をエッチングした後、残存するフォトレジスト膜を除去する一連の過程を多数回繰り返して形成することができるが、この過程で最少5回の露光、現像工程を進めることが一般的な技術である(5回の露光、現像工程によってTFT回路を得ることを5-Mask工程という)。 Currently, TFTs are mainly used in liquid crystal display device circuits. Such a TFT circuit uniformly coats or applies a photoresist composition for a liquid crystal display device circuit, exposes and develops the coated photoresist composition in the presence of a mask having a predetermined shape, After creating a pattern with the desired shape, the metal film or insulating film is etched using the patterned photoresist film as a mask, and then a series of processes for removing the remaining photoresist film are repeated many times. Although it can be formed, it is a general technique to advance the exposure and development process at least five times in this process (to obtain a TFT circuit by five exposure and development processes is called a 5-Mask process).
したがって、前記露光、現像工程の回数を減らすことにより生産収率を高めることができるが、1度の露光、現像工程で2回以上の露光、現像工程を行なって形成したように、現像後に残ったフォトレジストの高さが互いに異なる多層の残膜構造を得るのに有効なフォトレジスト組成物を適用することによる、最少1回以上の露光、現像工程回数を減らすことができる(4回の露光、現像工程によってTFT回路を得ることを4-Mask工程という)。このように特殊な機能を有するフォトレジストは既存の液晶表示装置回路用フォトレジストで重要視した露光部と非露光部間の現像速度の差による現像コントラストだけでなく、半露光部(half-tone部:Maskのdouble slit間隔調節や透過率調節を通じて露光部露光量と非露光部露光量の中間値を有する部分)の残膜均一度(Remain Film Thickness uniformity)が最も重要に要求される物性である。 Therefore, the production yield can be increased by reducing the number of times of the exposure and development process, but the residual after development as formed by performing the exposure and development process twice or more in one exposure and development process. Further, by applying a photoresist composition effective for obtaining a multi-layered residual film structure having different photoresist heights, the number of exposure and development processes can be reduced at least once (four exposures). And obtaining a TFT circuit by a development process is called a 4-Mask process). In this way, the photoresist having a special function is not only the development contrast due to the difference in the developing speed between the exposed part and the non-exposed part, which is important in the existing photoresist for liquid crystal display circuit, but also the half-tone part (half-tone part). Part: Remain Film Thickness uniformity is the most important property required by adjusting the double slit interval of Mask and the transmittance, and the part with the intermediate value between the exposure amount of the exposed part and the non-exposed part. is there.
感光速度は露光によって液晶表示装置回路用フォトレジストの溶解度が変わる速度のことを言い、反復工程によって多重パターンを生成させるために数回の露出が必要であったり、光が一連のレンズと単色フィルターを通過する投射露出技法のように強度が低下した光を使用するフォトレジスト膜において特に重要である。 Photosensitivity refers to the rate at which the solubility of the photoresist for liquid crystal display circuit circuits changes due to exposure, and several exposures are required to generate multiple patterns through repeated processes, or light is a series of lenses and monochromatic filters. This is particularly important in photoresist films that use light of reduced intensity, such as projection exposure techniques that pass through.
特に、薄膜トランジスタ液晶表示装置(以下、TFT-LCDと言う)の特徴である基板の大面積化による生産ラインでの長い露光時間を減らすためには感光速度の向上が必ず要求される。また、感光速度と残膜率は反比例関係で、感光速度が速いと残膜率は減少する傾向を示す。 In particular, in order to reduce the long exposure time on the production line due to the large area of the substrate, which is a feature of the thin film transistor liquid crystal display device (hereinafter referred to as TFT-LCD), it is necessary to improve the photosensitive speed. In addition, the photosensitive speed and the remaining film ratio are inversely proportional to each other, and when the photosensitive speed is high, the remaining film ratio tends to decrease.
現像コントラストは現像によって露出された部位でのフィルム損失量と露出されていない部位でのフィルム損失量の比を意味する。通常フォトレジスト膜で被覆された露出基板は露出部位の被覆物がほとんど完全に溶解されて除去されるまで継続して現像されるので、現像コントラストは露出された被覆部位が完全に除去される時、露出されていない部位でフィルム損失量を測定して簡単に決定できる。 The development contrast means the ratio of the film loss amount at a portion exposed by development to the film loss amount at a portion not exposed. Normally, an exposed substrate coated with a photoresist film is continuously developed until the coating on the exposed area is almost completely dissolved and removed, so that development contrast is achieved when the exposed coated area is completely removed. It can be easily determined by measuring the film loss at the unexposed part.
フォトレジスト膜の解像度はレジスト膜を露出させる時に使用したマスクの空間間隔によって微細な回路線が高度に鋭敏な像で示されるように再生させるレジスト膜システムの能力を意味する。 The resolution of the photoresist film means the ability of the resist film system to reproduce fine circuit lines so as to show a highly sensitive image according to the space interval of the mask used when exposing the resist film.
各種産業上の用途、特に液晶表示装置や半導体回路の製造において、液晶表示装置回路用フォトレジスト膜は非常に細い線と空間面積(10μm以下)を有するパターンが形成できる程度の解像度が必要である。 In various industrial applications, particularly in the manufacture of liquid crystal display devices and semiconductor circuits, the photoresist film for liquid crystal display device circuits needs to have a resolution that can form a pattern with very fine lines and a space area (10 μm or less). .
各種基板との接着力とは液晶表示装置回路用フォトレジスト組成物に要求される物性の一つで、金属膜または絶縁膜を湿式エッチングする時、基板上に微細回路におけるパターンの有無による選択性を増加させる役割を果たす。 Adhesive strength with various substrates is one of the physical properties required for photoresist compositions for liquid crystal display device circuits. When wet etching a metal film or insulating film, selectivity depending on the presence or absence of patterns in the microcircuit on the substrate It plays a role to increase.
大部分の液晶表示装置回路用フォトレジスト組成物はフォトレジスト膜を形成するための高分子樹脂、感光性化合物及び溶媒を含む。先行技術で液晶表示装置回路用フォトレジスト組成物の感光速度、現像コントラスト、解像度及び人体安全性を改善するための多くの試みが行なわれた。 Most of the photoresist compositions for liquid crystal display devices include a polymer resin, a photosensitive compound and a solvent for forming a photoresist film. Many attempts have been made in the prior art to improve the photosensitivity, development contrast, resolution and human safety of photoresist compositions for liquid crystal display circuits.
例えば、特許文献1には二つのフェノールフォルムアルデヒドノボラック樹脂の混合物と典型的な感光性化合物の使用が開示されており、特許文献2には感光速度を増加させるためにフェノール性樹脂とナフトキノンジアジド感光剤に有機酸サイクリック無水物を添加することが開示されており、特許文献3には感光速度を増加させて人体安全性を向上させるためにノボラック樹脂とo-キノンジアジド感光性化合物と溶媒としてプロピレングリコールアルキルエーテルアセテートの使用が開示されている。また、特許文献4には解像度及び耐熱性を増加させるためにノボラック樹脂を分級処理する方法の使用が開示されており、上記の内容は当分野の従事者には広く知られている。 For example, Patent Document 1 discloses the use of a mixture of two phenol formaldehyde novolak resins and a typical photosensitive compound, and Patent Document 2 discloses the use of a phenolic resin and a naphthoquinone diazide photosensitive material in order to increase the photosensitive speed. It is disclosed that an organic acid cyclic anhydride is added to an agent, and Patent Document 3 discloses a novolak resin, an o-quinonediazide photosensitive compound and propylene as a solvent in order to increase the photosensitive speed and improve human safety. The use of glycol alkyl ether acetate is disclosed. Patent Document 4 discloses the use of a method for classifying a novolak resin in order to increase resolution and heat resistance, and the above contents are widely known to those skilled in the art.
また、液晶表示装置回路用フォトレジスト組成物の物性向上及び作業安定性のために多様な溶媒が開発されたが、その例としてエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、乳酸エチルなどがある。 Various solvents have been developed to improve the physical properties and work stability of photoresist compositions for liquid crystal display device circuits. Examples include ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl lactate. There is.
しかし、まだ感光速度、残膜率、半露光部の残膜均一度、現像コントラスト、解像度、高分子樹脂の溶解性、基板との接着力、回路線幅均一度などのような液晶表示装置回路用フォトレジスト組成物の好ましい特性のうちいずれか一つの特性を犠牲にせずに各々の産業工程に適した多様な液晶表示装置回路用フォトレジスト組成物は開発されておらず、これに関する要求は続いている。
本発明は前記のような従来技術の問題点を考慮して、フォトレジスト膜の感光速度、残膜率、半露光部の残膜均一度、現像コントラスト、解像度、回路線幅均一度及び基板との接着力を向上させることができる新規組成の液晶表示装置回路用フォトレジスト組成物を提供することを目的とする。 The present invention takes into account the problems of the prior art as described above, and the photosensitive speed of the photoresist film, the remaining film rate, the remaining film uniformity of the half-exposed portion, the development contrast, the resolution, the circuit line width uniformity, and the substrate An object of the present invention is to provide a photoresist composition for a liquid crystal display device circuit having a novel composition capable of improving the adhesive strength of the liquid crystal display device.
本発明の他の目的は、前記フォトレジスト組成物を利用して製造される半導体素子を提供することにある。 Another object of the present invention is to provide a semiconductor device manufactured using the photoresist composition.
前記目的を達成するために本発明は、高分子樹脂、感光性化合物、密着増強剤及び有機溶媒を含む液晶表示装置回路用フォトレジスト組成物において、
(a)メタ/パラクレゾールの含量が50乃至80:50乃至20の重量部である数平均分子量5000〜9000のノボラック樹脂;(b)ジアジド系感光性化合物;(c)密着増強剤;及び(d)有機溶媒を含み、前記ジアジド系感光性化合物は2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩及び2,3,4-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩の混合物であり、前記有機溶媒が70乃至90:30乃至10の重量部で混合されるプロピレングリコールメチルエーテルアセテート(以下、PGMEAという)と2-メトキシ酢酸エチル(以下、MMPという)の混合物であることを特徴とする液晶表示装置回路用フォトレジスト組成物を提供する。
To achieve the above object, the present invention provides a photoresist composition for a liquid crystal display device circuit comprising a polymer resin, a photosensitive compound, an adhesion enhancer, and an organic solvent.
(A) a novolak resin having a number average molecular weight of 5000 to 9000 having a meta / paracresol content of 50 to 80:50 to 20 parts by weight; (b) a diazide-based photosensitive compound; (c) an adhesion enhancer; d) looking contains an organic solvent, wherein the diazide based photosensitive compound is 2,3,4,4-tetrahydroxy-benzophenone 1,2-naphthoquinonediazide-5-sulfonate and 2,3,4 -1,2-naphthoquinonediazide-5-sulfonate, a mixture of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) in which the organic solvent is mixed in an amount of 70 to 90:30 to 10 parts by weight; Provided is a photoresist composition for a circuit of a liquid crystal display device , which is a mixture of ethyl methoxyacetate (hereinafter referred to as MMP) .
本発明のフォトレジスト組成物は、(a)メタ/パラクレゾールの含量が50乃至65:50乃至35の重量部である数平均分子量6000〜7500のノボラック樹脂15乃至25重量%;(b)2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩と2,3,4、-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩の混合比率が10乃至40:90乃至60の重量部で混合されるジアジド系感光性化合物4乃至8重量%;(c)密着増強剤0.3乃至1重量%;及び(d)PGMEAとMMPの混合比率が75乃至90:25乃至10の重量部で混合される有機溶媒65乃至90重量%を含むことが好ましい。 The photoresist composition of the present invention comprises (a) 15 to 25% by weight of a novolak resin having a number average molecular weight of 6000 to 7500 and having a meta / paracresol content of 50 to 65:50 to 35 parts by weight; (b) 2 , 3,4,4'-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 2,3,4, -trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate 4 to 8% by weight of a diazide-based photosensitive compound mixed in a weight ratio of 10 to 40:90 to 60; (c) 0.3 to 1% by weight of an adhesion enhancer; and (d) a mixture of PGMEA and MMP. It is preferable to include 65 to 90% by weight of organic solvent mixed in a ratio of 75 to 90:25 to 10 parts by weight.
また、本発明は前記基材のフォトレジスト組成物を金属膜または絶縁膜にコーティングした後、露光及び現像してフォトレジストパターンを形成し、エッチング及びストリッピングして製造される半導体素子を提供する。この半導体素子としては、TFT-LCDであることが好ましい。 The present invention also provides a semiconductor device manufactured by coating a photoresist composition of the base material on a metal film or an insulating film, and then exposing and developing to form a photoresist pattern, etching and stripping. . The semiconductor element is preferably a TFT-LCD.
本発明の液晶表示装置回路用フォトレジスト組成物は、感光速度と残膜率が優れており、半露光部の残膜均一度、解像度、現像コントラスト、耐熱性、接着性及びストリッパーに対する溶解性が優れているので、実際産業現場に容易に適用でき、作業環境を良好に変化させることができる。 The photoresist composition for a liquid crystal display device circuit of the present invention has excellent photosensitive speed and residual film ratio, and the residual film uniformity of half-exposed areas, resolution, development contrast, heat resistance, adhesion and solubility in strippers. Since it is excellent, it can be easily applied to an actual industrial site and the working environment can be changed well.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は高分子樹脂としてメタ-及びパラ-クレゾールの含量調節で製造されたノボラック樹脂を用いてフォトレジスト膜の感光速度、残膜率、半露光部の残膜均一度、接着力などの物性を大きく向上させることができる液晶表示装置回路用フォトレジスト組成物に関する。 The present invention uses a novolak resin produced by adjusting the content of meta- and para-cresol as a polymer resin, and the physical properties such as the photosensitivity of the photoresist film, the remaining film ratio, the uniformity of the remaining film in the half-exposed area, and the adhesive strength The present invention relates to a photoresist composition for a circuit of a liquid crystal display device that can greatly improve the resistance.
前記液晶表示装置回路用フォトレジスト組成物を製造するために用いることができる高分子樹脂は当該分野に広く知られているが、本発明はその中でも前記のノボラック樹脂を使用する。前記ノボラック樹脂はメタ及び/またはパラクレゾールなどの芳香族アルコールとフォルムアルデヒドを反応させて合成した高分子重合体である。 Polymer resins that can be used for producing the photoresist composition for a liquid crystal display device circuit are widely known in the art, and the present invention uses the above-mentioned novolak resin among them. The novolak resin is a polymer synthesized by reacting an aromatic alcohol such as meta and / or paracresol with formaldehyde.
前記ノボラック樹脂はメタ/パラクレゾールの高分子重合体の混合比によって感光速度と残膜率、半露光部の残膜均一度などの物性が左右される。また、液晶表示装置回路用フォトレジスト組成物において、ハードベーク工程後にパターンの熱による流動が起こるが、このような熱流動はメタクレゾールとパラクレゾールの比率を適切に調節あるいは高分子重合体の分子量を調節して気体プラズマで処理すれば、基板の線幅と傾斜を調節することができる。 The properties of the novolak resin, such as the photosensitivity and the remaining film ratio, and the uniformity of the remaining film in the half-exposed portion, are affected by the mixing ratio of the meta / paracresol polymer. Also, in the photoresist composition for liquid crystal display device circuits, pattern heat flow occurs after the hard baking process. Such heat flow can be achieved by appropriately adjusting the ratio of metacresol and paracresol or the molecular weight of the polymer. If the substrate is treated with gas plasma, the line width and inclination of the substrate can be adjusted.
したがって、本発明のフォトレジスト組成物において、(a)高分子樹脂はノボラック樹脂を含み、さらに好ましくはメタ/パラクレゾールの含量が50乃至80:50乃至20の重量部の比率で製造された数平均分子量5000〜9000のノボラック樹脂を使用する。この時、前記メタクレゾールの含量が前記範囲を超えれば、感光速度が速くなって残膜率が急激に低くなり、パラクレゾールの含量が前記範囲を超えると感光速度が遅くなる短所がある。 Accordingly, the photoresist composition of the present invention, (a) Number polymer resin comprises a novolak resin, more preferably prepared at a ratio of parts by weight of meta / content of para-cresol 50 to 80:50 to 20 A novolak resin having an average molecular weight of 5000 to 9000 is used. At this time, if the content of metacresol exceeds the above range, the photosensitivity increases and the remaining film rate decreases rapidly. If the content of paracresol exceeds the above range, the photosensitivity decreases.
本発明で使用する高分子樹脂の含量は5乃至30重量%として用い、前記高分子樹脂の含量が5重量%未満であれば粘度があまり低すぎるため所望の厚さの塗布に問題点があり、30重量%を超えると粘度が高すぎるため基板の均一なコーティングが難しい問題点がある。 The content of the polymer resin used in the present invention is 5 to 30% by weight, and if the content of the polymer resin is less than 5% by weight, the viscosity is too low and there is a problem in coating with a desired thickness. If it exceeds 30% by weight, the viscosity is too high, so that there is a problem that it is difficult to uniformly coat the substrate.
前記(b)感光性化合物はジアジド系化合物としてトリヒドロキシベンゾフェノンと2-ジアゾ-1-ナフトール-5-スルホン酸をエステル化反応させて製造された2,3,4-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩とテトラヒドロキシベンゾフェノンと2-ジアゾ-1-ナフトール-5-スルホン酸をエステル化反応させて製造された2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩を単独または混合して用いることができる。 The (b) photosensitive compound is a 2,3,4-trihydroxybenzophenone-1,2 produced by esterification of trihydroxybenzophenone and 2-diazo-1-naphthol-5-sulfonic acid as a diazide compound. 2,3,4,4′-Tetrahydroxybenzophenone-1, produced by esterification of 2-naphthoquinonediazide-5-sulfonate, tetrahydroxybenzophenone and 2-diazo-1-naphthol-5-sulfonic acid 2-Naphthoquinonediazide-5-sulfonate can be used alone or in combination.
前記ジアジド系感光性化合物はポリヒドロキシベンゾフェノンと1,2-ナフトキノンジアジド、2-ジアゾ-1-ナフトール-5-スルホン酸などのジアジド系化合物を反応させて製造することができる。 The diazide photosensitive compound can be produced by reacting polyhydroxybenzophenone with a diazide compound such as 1,2-naphthoquinonediazide and 2-diazo-1-naphthol-5-sulfonic acid.
また、本発明で感光性化合物を利用して感光速度を調節するための2種類の方法としては感光性化合物の量を調節する方法と、2,3,4-トリヒドロキシベンゾフェノンあるいは2,3,4,4’-テトラヒドロキシベンゾフェノンと2-ジアゾ-1-ナフトール-5-スルホン酸のエステル化反応度を調節する方法がある。 In the present invention, two methods for adjusting the photosensitive speed using the photosensitive compound include a method of adjusting the amount of the photosensitive compound, 2,3,4-trihydroxybenzophenone, or 2,3,3. There is a method for adjusting the degree of esterification of 4,4′-tetrahydroxybenzophenone and 2-diazo-1-naphthol-5-sulfonic acid.
さらに好ましくは、前記感光性化合物として2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩及び2,3,4-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩の混合物を含むのが好ましく、二つの化合物の混合比率は10乃至60:90乃至40重量部で混合されるのが良い。 More preferably, the photosensitive compound is 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 2,3,4-trihydroxybenzophenone-1,2-naphtho. It is preferable to include a mixture of quinonediazide-5-sulfonate, and the mixing ratio of the two compounds is 10 to 60:90 to 40 parts by weight.
前記感光性化合物の含量は2乃至10重量%であり、前記感光性化合物の含量が2重量%未満であれば感光速度があまりに速くなって残膜率の激しい低下による問題点があり、10重量%を超えれば感光速度があまりに遅くなる問題点がある。 The photosensitive compound content is 2 to 10% by weight. If the photosensitive compound content is less than 2% by weight, the photosensitive speed is too high, and there is a problem that the remaining film ratio is drastically reduced. If the ratio exceeds 50%, the photosensitive speed becomes too slow.
また、本発明のフォトレジスト組成物において、(c)密着増強剤はコーティングまたは塗布されたフォトレジストの下部膜に対する密着特性を向上させるために用いる。前記密着増強剤は一般的なメラミン誘導体で複数のアミノ基が置換された化合物であるのが好ましく、さらに好ましくはメラミン誘導体に3乃至6のアミノ基が置換された化合物を用い、例えば、ヘキサメトキシメチルメラミンを用いることができる。 In the photoresist composition of the present invention, (c) an adhesion enhancer is used to improve adhesion characteristics of the coated or applied photoresist to the lower film. The adhesion enhancer is preferably a compound in which a plurality of amino groups are substituted with a general melamine derivative, and more preferably a compound in which 3 to 6 amino groups are substituted on the melamine derivative. Methyl melamine can be used.
前記密着増強剤の含量は0.1乃至1重量%用い、前記密着増強剤の含量が0.1重量%未満であればフォトレジストと下部膜との密着特性が低下してエッチング工程に問題点があり、1重量%を超えればフォトレジストを除去するストリップ工程が難しくなる問題点がある。 If the content of the adhesion enhancer is 0.1 to 1% by weight, and the content of the adhesion enhancer is less than 0.1% by weight, the adhesion characteristics between the photoresist and the lower film are deteriorated, which causes a problem in the etching process. If the amount exceeds 1% by weight, the strip process for removing the photoresist becomes difficult.
また、本発明のフォトレジスト組成物は(d)の有機溶媒を含み、好ましくは有機溶媒60乃至90重量%を含む。前記有機溶媒は具体的には、PGMEAを単独使用したりまたはPGMEAとEL、MMP、PGMEなどを混合して用いることができ、さらに好ましくはPGMEAとMMPを混合比率70乃至90:30乃至10の重量部で混合使用する。 The photoresist composition of the present invention contains the organic solvent (d), preferably 60 to 90% by weight of the organic solvent. Specifically, the organic solvent can be used by using PGMEA alone or by mixing PGMEA and EL, MMP, PGME, etc., more preferably PGMEA and MMP in a mixing ratio of 70 to 90:30 to 10. Mix by weight.
この他に、本発明の液晶表示装置回路用フォトレジスト組成物は必要に応じて着色剤、染料、擦痕防止剤、可塑剤、接着促進剤、界面活性剤などの添加剤を追加的に添加して基板に被覆することにより個別工程の特性による性能向上を図ることもできる。 In addition, the liquid crystal display device circuit photoresist composition of the present invention additionally includes additives such as colorants, dyes, anti-scratch agents, plasticizers, adhesion promoters, and surfactants as necessary. By covering the substrate, the performance can be improved by the characteristics of the individual process.
また、本発明は前記のように製造された液晶表示装置回路用フォトレジスト組成物を利用して半導体素子を製造することができる。半導体素子のうちの好ましい一例を挙げると、以下のようにして液晶表示装置回路の製造工程で用いることができる。 In addition, the present invention can manufacture a semiconductor element using the photoresist composition for a liquid crystal display device manufactured as described above. As a preferred example of the semiconductor element, it can be used in the manufacturing process of a liquid crystal display device circuit as follows.
本発明は前記液晶表示装置回路用フォトレジスト組成物を浸漬、噴霧、回転及びスピンコーティングを含む通常の方法で基板に塗布する。例えば、スピンコーティングする場合、液晶表示装置回路用フォトレジスト溶液の固体含量をスピニング装置の種類と方法によって適切に変化させることにより、目的とする厚さの被覆物を形成することができる。 In the present invention, the photoresist composition for a liquid crystal display device circuit is applied to a substrate by a usual method including dipping, spraying, rotation, and spin coating. For example, in the case of spin coating, a coating having a desired thickness can be formed by appropriately changing the solid content of the photoresist solution for a liquid crystal display device circuit according to the type and method of the spinning device.
前記基板としてはシリコン、アルミニウム、インジウムティンオキシド(ITO)、インジウムジンクオキシド(IZO)、モリブデン、クロム、二酸化シリコン、ドーピングされた二酸化シリコン、窒化シリコン、タンタル、銅、ポリシリコン、セラミック、アルミニウム/銅混合物及び各種重合性樹脂で構成されるものが含まれる。 The substrates include silicon, aluminum, indium tin oxide (ITO), indium zinc oxide (IZO), molybdenum, chromium, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramic, aluminum / copper Those composed of a mixture and various polymerizable resins are included.
前記方法によって基板にコーティングされた液晶表示装置回路用フォトレジスト組成物を80乃至130℃の温度で加熱するが、これをソフトベーク工程と言う。このような熱処理は液晶表示装置回路用フォトレジスト組成物のうちの固体成分を熱分解させずに、溶媒を蒸発させるために行う。一般にソフトベーク工程によって溶媒の濃度を最少化することが好ましいので、このような熱処理は大部分の溶媒が蒸発して厚さ3μm以下の液晶表示装置回路用フォトレジスト組成物の薄い被覆膜が基板に残るまで行なう。 The photoresist composition for a liquid crystal display device circuit coated on the substrate by the above method is heated at a temperature of 80 to 130 ° C. This is called a soft baking process. Such heat treatment is performed in order to evaporate the solvent without thermally decomposing solid components in the photoresist composition for liquid crystal display device circuits. In general, it is preferable to minimize the concentration of the solvent by a soft baking process. Therefore, in such a heat treatment, a thin coating film of a photoresist composition for a liquid crystal display device circuit having a thickness of 3 μm or less is obtained by evaporating most of the solvent. Continue until it remains on the substrate.
次に、フォトレジスト膜が形成された基板を適当なマスクまたは型板などを使用して光、特に紫外線に露光させることにより、目的とする形態のパターンを形成する。その次に、露光された基板をアルカリ性現像水溶液に十分に浸漬させた後、光に露出された部位のフォトレジスト膜が全部または大部分溶解されるまで放置する。前記アルカリ性現像水溶液としてはアルカリ水酸化物、水酸化アンモニウムまたはテトラメチルアンモニウムヒドロキシドを含む水溶液などを用いることができる。 Next, the substrate on which the photoresist film is formed is exposed to light, particularly ultraviolet rays, using an appropriate mask or a template, thereby forming a pattern of a desired form. Next, the exposed substrate is sufficiently immersed in an alkaline developing aqueous solution, and then left to stand until all or most of the photoresist film exposed to light is dissolved. As the alkaline developing aqueous solution, an aqueous solution containing an alkali hydroxide, ammonium hydroxide or tetramethylammonium hydroxide can be used.
また、本発明は露光された部位が溶解されて除去された基板を現像液から取り出した後、再び熱処理してフォトレジスト膜の接着性及び耐化学性を増進させることができるが、これを一般にハードベーク工程と言う。このような熱処理はフォトレジスト膜の軟化点以下の温度で行われ、好ましくは90乃至140℃の温度で行うことができる。 In addition, the present invention can improve the adhesion and chemical resistance of the photoresist film by removing the substrate from which the exposed portion has been dissolved and removed from the developer, and then heat-treating it again. This is called a hard baking process. Such heat treatment is performed at a temperature below the softening point of the photoresist film, and preferably at a temperature of 90 to 140 ° C.
このように現像が完了した基板を腐蝕溶液または気体プラズマで処理して露出された基板部位を処理し、この時、基板の露出されていない部位はフォトレジスト膜によって保護される。このように基板を処理した後、適切なストリッパーでフォトレジスト膜を除去することにより基板に微細回路パターンを形成する。 In this way, the exposed substrate portion is processed by treating the developed substrate with a corrosive solution or gas plasma, and at this time, the unexposed portion of the substrate is protected by the photoresist film. After processing the substrate in this way, a fine circuit pattern is formed on the substrate by removing the photoresist film with an appropriate stripper.
以下の実施例及び比較例を通じて本発明をさらに詳細に説明する。但し、下記の実施例は本発明を例示するためのものに過ぎず、本発明が下記実施例によって限られるわけではない。 The present invention will be described in more detail through the following examples and comparative examples. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples.
(メタ/パラノボラック樹脂の合成)
[比較合成例1]
オ−バ−ヘッド撹拌機にメタクレゾール40g、パラクレゾール60g、フォルムアルデヒド65g、シュウ酸0.5gを入れ、攪拌して均質混合物を製造した。反応混合物を95℃で加熱し、この温度を4時間維持した。還流コンデンサーを蒸留装置で代替し、反応混合物の温度を110℃で2時間蒸留した。真空蒸留を180℃で2時間行なって残余単量体を蒸留除去しており、溶融されたノボラック樹脂を室温に冷却した。GPCで数平均分子量を測定して分子量4800のノボラック樹脂を得た(ポリスチレン基準)。
(Synthesis of meta / paranovolak resin)
[Comparative Synthesis Example 1]
An overhead stirrer was charged with 40 g of metacresol, 60 g of paracresol, 65 g of formaldehyde, and 0.5 g of oxalic acid, and stirred to produce a homogeneous mixture. The reaction mixture was heated at 95 ° C. and this temperature was maintained for 4 hours. The reflux condenser was replaced with a distillation apparatus, and the temperature of the reaction mixture was distilled at 110 ° C. for 2 hours. Vacuum distillation was performed at 180 ° C. for 2 hours to distill off the remaining monomers, and the molten novolak resin was cooled to room temperature. The number average molecular weight was measured by GPC to obtain a novolak resin having a molecular weight of 4800 (polystyrene basis).
[比較合成例2]
前記比較合成例1と同様な方法で合成するものの、メタクレゾール85g、パラクレゾール15g、フォルムアルデヒド65g、及びシュウ酸0.5gを使用して数平均分子量9600のノボラック樹脂を得た(ポリスチレン基準)。
[Comparative Synthesis Example 2]
Although synthesized by the same method as in Comparative Synthesis Example 1, a novolak resin having a number average molecular weight of 9600 was obtained using 85 g of metacresol, 15 g of paracresol, 65 g of formaldehyde, and 0.5 g of oxalic acid (polystyrene basis). .
[合成例1]
前記比較合成例1と同様な方法で合成するものの、メタクレゾール55g、パラクレゾール45g、フォルムアルデヒド65g、及びシュウ酸0.5gを使用して数平均分子量6300のノボラック樹脂を得た(ポリスチレン基準)。
[Synthesis Example 1]
Although synthesized by the same method as in Comparative Synthesis Example 1, 55 g of metacresol, 45 g of paracresol, 65 g of formaldehyde, and 0.5 g of oxalic acid were used to obtain a novolak resin having a number average molecular weight of 6300 (polystyrene basis). .
[実施例1]
感光剤5.5g、前記合成例1で得たノボラック樹脂20g、密着増強剤であるヘキサメトキシメチルメラミン0.5gに有機溶媒としてPGMEA56g、MMP14gを投入して常温で40rpmで攪拌し、液晶表示装置回路用フォトレジスト組成物を製造した。前記感光剤は2,3,4-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩と2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩が9/1で混合された混合物を使用した。
[Example 1]
5.5 g of the photosensitizer, 20 g of the novolak resin obtained in Synthesis Example 1 above, 0.5 g of hexamethoxymethylmelamine as the adhesion enhancer, and 56 g of PGMEA and 14 g of MMP as organic solvents were added and stirred at room temperature at 40 rpm. A circuit photoresist composition was prepared. The sensitizers are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone. A mixture of 9/1 acid salt was used.
前記で製造された液晶表示装置回路用フォトレジスト組成物を0.7T(thickness、0.7mm)のガラス基板に滴下し、一定の回転速度で回転させた後、前記基板を110℃で90分間加熱乾燥し、2.40μm厚さのフィルム膜を形成した。前記フィルム膜上に所定の形状のマスクを装着した後、紫外線を照射し、テトラメチルアンモニウムヒドロキシド2.38重量%水溶液に70秒間浸漬し、紫外線に露光された部分を除去してフォトレジストパターンを形成した。このようなパターンをCrガラス上に形成し、これを腐蝕溶液で処理して腐蝕溶液に露出されていないCrを腐蝕した長さを測定した。 The liquid crystal display device photoresist composition manufactured as described above is dropped on a 0.7T (thickness, 0.7 mm) glass substrate and rotated at a constant rotation speed, and then the substrate is heated at 110 ° C. for 90 minutes. Heat drying was performed to form a film film having a thickness of 2.40 μm. A mask having a predetermined shape is mounted on the film film, and then irradiated with ultraviolet light, immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 70 seconds, and a portion exposed to the ultraviolet light is removed to form a photoresist pattern. Formed. Such a pattern was formed on Cr glass, and this was treated with a corrosive solution to measure the length of the corroded Cr not exposed to the corrosive solution.
[比較例1]
前記実施例1と同様な方法で製造するものの、比較合成例1で得たノボラック樹脂を使用して液晶表示装置回路用フォトレジスト組成物を製造した。
[Comparative Example 1]
Although manufactured by the same method as in Example 1, a novolak resin obtained in Comparative Synthesis Example 1 was used to manufacture a photoresist composition for a liquid crystal display device circuit.
[比較例2]
前記実施例1と同様な方法で製造するものの、比較合成例2で得たノボラック樹脂を使用して液晶表示装置回路用フォトレジスト組成物を製造した。
[Comparative Example 2]
Although manufactured by the same method as in Example 1, a novolak resin obtained in Comparative Synthesis Example 2 was used to manufacture a photoresist composition for a liquid crystal display device circuit.
[比較例3]
前記実施例1と同様な方法で製造するものの、合成例1で得たノボラック樹脂を使用して2,3,4-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩を単独で使用して液晶表示装置回路用フォトレジスト組成物を製造した。
[Comparative Example 3]
Although produced by the same method as in Example 1, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate was used alone using the novolak resin obtained in Synthesis Example 1. A photoresist composition for a liquid crystal display device circuit was produced.
[比較例4]
前記実施例1と同様な方法で製造するものの、合成例1で得たノボラック樹脂を使用し、2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩を単独で使用して液晶表示装置回路用フォトレジスト組成物を製造した。
[Comparative Example 4]
Although manufactured by the same method as in Example 1, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate is used using the novolak resin obtained in Synthesis Example 1. Was used alone to produce a photoresist composition for liquid crystal display device circuits.
[試験例]
前記実施例1及び比較例1乃至4で製造されたフォトレジスト組成物に対して次のような方法で物性を測定し、その結果を下記表1に示した。
[Test example]
The physical properties of the photoresist compositions prepared in Example 1 and Comparative Examples 1 to 4 were measured by the following method. The results are shown in Table 1 below.
A.感光速度と残膜率
感光速度は露光エネルギーによって一定の現像条件で膜が完全に溶けるエネルギーを測定して求めており、110℃でソフトベークを行って、露光及び現像した後、数式1及び2により残膜率を測定した。
[数式1]
初期フィルム厚さ=損失厚さ+残膜厚さ
[数式2]
残膜率=(残膜厚さ/初期フィルム厚さ)
B.半露光部の残膜均一度
マスクパターンのダブルスリット間隔によって現像工程後にも半露光部に残っている残膜厚さ(RFT)の均一な程度を下記数式3により測定した。
[数式3]
ΔRFT(Å)=|RFT(avg.)-RFT(x)|
前記式で、RFT(avg.)は全半露光部の平均残膜厚さであり、RFT(x)は任意の位置での半露光部の残膜厚さである。
A. Photosensitivity and remaining film rate The photosensitivity is obtained by measuring the energy at which a film is completely dissolved under a constant development condition depending on the exposure energy. After exposure to light and development by performing soft baking at 110 ° C., Equation 1 And 2 were used to measure the remaining film ratio.
[Formula 1]
Initial film thickness = loss thickness + residual film thickness
[Formula 2]
Residual film rate = (Residual film thickness / Initial film thickness)
B. Residual film uniformity in half-exposed area The degree of uniformity of the residual film thickness (RFT) remaining in the semi-exposed area even after the development process was measured by the following Equation 3 by the double slit interval of the mask pattern.
[Formula 3]
ΔRFT (Å) = | RFT (avg.) − RFT (x) |
In the above equation, RFT (avg.) Is the average remaining film thickness of the entire half-exposed area, and RFT (x) is the remaining film thickness of the semi-exposed area at an arbitrary position.
C.耐熱性
耐熱性はDSCでTg(Glass Transition Temperature:ガラス転移温度)を測定した。
C. Heat resistance Tg (Glass Transition Temperature) was measured by DSC.
D.接着性
Crがコーティングされたガラス上に液晶表示装置回路用フォトレジスト組成物により製造されたフォトレジスト膜は現像工程で所望のパターン(微細線幅)を得た後、露出された部位のCrを除去するために腐蝕溶液で処理し、腐蝕溶液に露出されていないCrを腐蝕した長さを測定して接着性を試験した。
D. Adhesive A photoresist film manufactured with a photoresist composition for a liquid crystal display device circuit on glass coated with Cr has a desired pattern (fine line width) obtained in a development process, and then the exposed portion of Cr is applied. In order to remove it, it was treated with a corrosive solution, and the adhesion was tested by measuring the length of the corroded Cr not exposed to the corrosive solution.
また、実施例1のフォトレジスト組成物によって製造されたフォトレジスト膜の感光エネルギーは従来法による比較例1乃至4と比較して同等な水準での残膜率が高い値を有することが分かる。 Further, it can be seen that the photosensitive energy of the photoresist film manufactured by the photoresist composition of Example 1 has a high value of the residual film ratio at the same level as compared with Comparative Examples 1 to 4 by the conventional method.
また、本発明の液晶表示装置回路用フォトレジスト組成物によって製造されたフォトレジスト膜は従来の液晶表示装置回路用フォトレジスト組成物によって製造されたフォトレジスト膜より液晶表示装置回路用フォトレジストの残留膜が多く残ってフォトレジスト膜としての物性が従来比較例より優れていることが分かる。 In addition, the photoresist film manufactured using the photoresist composition for a liquid crystal display device circuit according to the present invention is a residue of the photoresist for the liquid crystal display device circuit than the photoresist film manufactured using the conventional photoresist composition for a liquid crystal display device circuit. It can be seen that many films remain and the physical properties as a photoresist film are superior to those of the conventional comparative example.
さらに、前記表1に示すように、実施例1のフォトレジスト組成物によって製造されたフォトレジスト膜は現像工程で所望のパターン(微細線幅)を得た後、ハードベーク工程で接着性の向上とパターンプロファイルの変化を期待することができる。 Furthermore, as shown in Table 1 above, the photoresist film manufactured with the photoresist composition of Example 1 has improved adhesion in the hard baking process after obtaining a desired pattern (fine line width) in the development process. And you can expect changes in the pattern profile.
Claims (7)
(a)メタ/パラクレゾールの含量が50乃至80:50乃至20の重量部である数平均分子量5000〜9000のノボラック樹脂;(b)ジアジド系感光性化合物;(c)密着増強剤;及び(d)有機溶媒を含み、
前記ジアジド系感光性化合物は2,3,4,4’-テトラヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩及び2,3,4-トリヒドロキシベンゾフェノン-1,2-ナフトキノンジアジド-5-スルホン酸塩の混合物であり、
前記有機溶媒が70乃至90:30乃至10の重量部で混合されるプロピレングリコールメチルエーテルアセテート(以下、PGMEAという)と2-メトキシ酢酸エチル(以下、MMPという)の混合物であることを特徴とする液晶表示装置回路用フォトレジスト組成物。 In a photoresist composition for a liquid crystal display device circuit comprising a polymer resin, a photosensitive compound, an adhesion enhancer and an organic solvent,
(A) a novolak resin having a number average molecular weight of 5000 to 9000 having a meta / paracresol content of 50 to 80:50 to 20 parts by weight; (b) a diazide-based photosensitive compound; (c) an adhesion enhancer; viewing including the d) organic solvent,
The diazide-based photosensitive compound includes 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide— A mixture of 5-sulfonates,
The organic solvent is a mixture of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) and ethyl 2-methoxyacetate (hereinafter referred to as MMP) mixed in 70 to 90:30 to 10 parts by weight. Photoresist composition for liquid crystal display device circuit.
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