JPS5859443A - Positive type radiation-sensitive resist material - Google Patents
Positive type radiation-sensitive resist materialInfo
- Publication number
- JPS5859443A JPS5859443A JP15820481A JP15820481A JPS5859443A JP S5859443 A JPS5859443 A JP S5859443A JP 15820481 A JP15820481 A JP 15820481A JP 15820481 A JP15820481 A JP 15820481A JP S5859443 A JPS5859443 A JP S5859443A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- resist material
- halogen
- acid copolymer
- contg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 36
- 230000005855 radiation Effects 0.000 title claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 22
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 7
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000010894 electron beam technology Methods 0.000 abstract description 4
- BOASSOYETJYEJF-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-chloroprop-2-enoate Chemical compound FC(F)(F)COC(=O)C(Cl)=C BOASSOYETJYEJF-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010884 ion-beam technique Methods 0.000 abstract description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 abstract 2
- FMRJVEQQDQDHTK-UHFFFAOYSA-N 3,3-difluoropropyl 2-chloroprop-2-enoate Chemical compound FC(CCOC(C(=C)Cl)=O)F FMRJVEQQDQDHTK-UHFFFAOYSA-N 0.000 abstract 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- 238000005530 etching Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- JINLXNKYCADLRM-UHFFFAOYSA-N propan-2-yl 2-fluoroprop-2-enoate Chemical compound CC(C)OC(=O)C(F)=C JINLXNKYCADLRM-UHFFFAOYSA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Abstract
Description
【発明の詳細な説明】
本発明は、フォトマスクや半導体集積回路等の微細回路
パターンを形成するときに使用するポジ型放射線感応レ
ジスト材料、更憂こ祥しくは高感度、高解像性であり、
更には基板との密着性にすぐれたポジ型放射線感応レジ
スト材料に関する〇半導体素子等の高密度化・高集積化
のすう勢に対処するため、従来用いてきた紫外光よりも
更に波長が短い電子ビーム、Ｘ、線又はイオンビーム等
の高エネルギー放射、線を照射して、一層黴細な回路パ
ターンを形成する方法が試みられている。[Detailed Description of the Invention] The present invention relates to a positive radiation-sensitive resist material used when forming fine circuit patterns such as photomasks and semiconductor integrated circuits, which has high sensitivity and high resolution. can be,
Furthermore, regarding positive-type radiation-sensitive resist materials with excellent adhesion to substrates, in order to cope with the trend toward higher density and higher integration of semiconductor devices, electron beams with a wavelength shorter than the conventional ultraviolet light have been developed. Attempts have been made to form finer circuit patterns by irradiating high-energy radiation such as , X, rays, or ion beams.
ところで、このような回路パターンの形成法において用
いられるレジスト材料には、高精度な回路パターンを迅
速に形成するという観点からして、抜ず、高感度、高解
像性という特性が必要とされる？更には、エツチング等
の玉揚において、形成したレジスト層が保１ｌｌＩ膜と
しての機能と耐性を備えることが必要とするので、上記
特性に加えて、耐エツチング性、密着性という特性も必
要となる。By the way, the resist materials used in such circuit pattern forming methods are required to have the characteristics of non-cutting, high sensitivity, and high resolution from the viewpoint of quickly forming highly accurate circuit patterns. Ru? Furthermore, in doffing such as etching, the formed resist layer needs to have the function and resistance as a protective film, so in addition to the above properties, properties such as etching resistance and adhesion are also required. .
従来から、多くのポジ型放射線感応レジスト材料が知ら
れているが、いずれも上記した特性の全てを満足するも
のではない。例えば、代表的なポジ型電子ビームレジス
ト材料として知られているポリブテン−１−スルホン（
ＰＢＳ ）は、ポジ匿材料の中ではレジスト感度が高く
、才た、ネガ型材料に比べてその解像性が２〜５倍優れ
てはいるが、耐エツチング性、密着性という特性面にお
いては著しく劣っている。このため、ドライエツチング
工程において、熱安定性が悪いということと相俟って保
＠膜としての耐性は充分に大きくない０また、浸酸化学
エッチング工程においては、フォトマスクや牛導体基板
との密着性が悪いため、非パターン領域にまでエツチン
グ液が浸透してしまい、高精度な回路パターンの形成が
困難になる。Although many positive radiation-sensitive resist materials have been known, none of them satisfy all of the above characteristics. For example, polybutene-1-sulfone (
PBS) has high resist sensitivity among positive-tone materials, and its resolution is 2 to 5 times better than negative-tone materials, but it lacks in terms of properties such as etching resistance and adhesion. Significantly inferior. For this reason, in the dry etching process, combined with poor thermal stability, the resistance as a protective film is not sufficiently high.In addition, in the immersion chemical etching process, it is difficult to bond with photomasks and conductive substrates. Due to poor adhesion, the etching solution penetrates into non-pattern areas, making it difficult to form highly accurate circuit patterns.
通常、レジスト材料と下地基材との密着性の程度は、例
えば浸式化学エツチング法で下地基材を加工する際に、
レジストの端部と下地基材との接触部壷〔おけるエツチ
ング液の浸透の程度をパターン変換差として測定するこ
とによって評価されている。すなわち、両者の密着性が
良好な場合には、エツチング処理後の下地基材の寸法と
レジストパターンの寸法との差は極めて小さいが、密着
性が不良の場合に（ま、エツチング液の浸透が両者の接
触部において非所望領域にまで拡大し、その結果、加工
された下地基材の寸法はレジストパターンの寸法より大
きくなって設計寸法からの偏差が著しく大きくなる０す
なわち、密着性が悪いと、回路パターンの精度が低下す
ることになる。Normally, the degree of adhesion between the resist material and the base material is determined by, for example, when processing the base material by immersion chemical etching.
It is evaluated by measuring the degree of penetration of the etching solution in the contact area between the edge of the resist and the underlying substrate as a difference in pattern conversion. In other words, when the adhesion between the two is good, the difference between the dimensions of the underlying substrate after etching and the dimensions of the resist pattern is extremely small, but when the adhesion is poor (well, the penetration of the etching solution is The contact area between the two expands to an undesired area, and as a result, the dimensions of the processed underlying base material become larger than the dimensions of the resist pattern, resulting in a significant deviation from the design dimension. In other words, the adhesion is poor. , the accuracy of the circuit pattern will decrease.
近時、上記したＰＢＳよりも一層高感度でかつ高解像性
のハロゲン含有ポジ型レジスト材料が開示されている（
特開昭５５−１８６３８号）。Recently, halogen-containing positive resist materials have been disclosed that have higher sensitivity and higher resolution than the above-mentioned PBS (
JP-A-55-18638).
この材料（工、ａ鎖にエステル、主鎖のα位にフッ素、
＠素等を３Ｍするアクリレート誘導体であって、・ｆジ
型放射線感応レジストとして用いることができる。This material (engineering, ester in the a chain, fluorine in the α position of the main chain,
It is an acrylate derivative containing 3M of @ element, etc., and can be used as a .f di-type radiation-sensitive resist.
しかしながら、これらのハロゲン含有のアクリル酸エス
テル−導体のレジストの多くは撥水性であり、したがっ
て、マスク基板及Ｏ牛導体基材との密着性に関しては難
点がある。また、酸性溶液による浸酸化学エッチング工
程においては、すぐれた耐酸性を示す反面、撥水性なの
でエツチングが不均一かつ不完全にしか行なえないとい
う不都合がある。However, many of these halogen-containing acrylic acid ester conductor resists are water repellent, and therefore have difficulties in adhesion to mask substrates and conductor substrates. Further, in the immersion chemical etching step using an acidic solution, although it exhibits excellent acid resistance, it has the disadvantage that etching can only be performed unevenly and incompletely because of its water repellency.
これらのレジストは、感度、解像性は良好でありまたＰ
ＢＳに比べて熱的安定性にも優れているので、密着性の
向上を図れば微細回路ｔ４ターン形成工程に有効に使用
し得るものと考えられる。These resists have good sensitivity and resolution, and P
Since it has superior thermal stability compared to BS, it is thought that it can be effectively used in the process of forming t4 turns of fine circuits if the adhesion is improved.
さて、レジスト材料の密着性に関しては、レジスト−基
板間の相互作用、すなわち、表面化学的な親和性（ぬれ
性）が大きく影響する。マスク基板、牛導体基材の表面
は、通常、吸着水分子、水酸基等で後われているため、
そもそも有機高分子であるレジスト材料との親和性は小
さい。このため、レジスト−基板間の密着性を向上せし
めるために、従来は、基板を加熱する脱水前処理、又は
シランカップリング剤等の接着促進剤を用いた表面処理
などが施されてきた０゛シかしながら、このような表面
処理を施した基板であっても、特開昭５５−１８６３８
号で開示されているようなハロゲン含有アクリル酸エス
テル誘導体のレジストにあっては、基板とのＷｉ着性は
顕著に改善されない。これは、上記レジスト材料の化学
組成そのものに基因するものと思われる。Now, the adhesion of a resist material is greatly influenced by the interaction between the resist and the substrate, that is, the surface chemical affinity (wettability). The surfaces of mask substrates and conductor substrates are usually covered with adsorbed water molecules, hydroxyl groups, etc.
In the first place, it has little affinity with resist materials that are organic polymers. Therefore, in order to improve the adhesion between the resist and the substrate, conventional methods include pre-dehydration treatment by heating the substrate, or surface treatment using an adhesion promoter such as a silane coupling agent. However, even with such a surface-treated substrate, Japanese Patent Laid-Open No. 55-18638
In the resist of a halogen-containing acrylic ester derivative as disclosed in the above publication, the Wi adhesion to the substrate is not significantly improved. This seems to be due to the chemical composition of the resist material itself.
ところ、で、固体表面の親和性（ぬれ性）の程度を表示
するものとして、ツイースマン（Ｚｉｓｍａｎ ）がア
ドバンスト・ケミカル・シリーズ、４３巻、１頁（１９
６４年） （Ａｄｖａｔ＋ｃ＠ｄ Ｃｈ＠ｍ１ａａ１
Ｂ＠ｒｌｅａ。By the way, as a means of indicating the degree of affinity (wettability) of a solid surface, Zisman (Advanced Chemical Series, Volume 43, Page 1 (19
64) (Advat+c@d Ch@m1aa1
B@rlea.
Ｖｏｌ ４３、ｐｐｌ （１９６４） ”）で提案した
臨界表面強力（ｒｏ）の概念が用いられている。これを
レジスト−基板間の密着性の問題に適用すると、レジス
ト材料（高分子）の接着力と１０ との間には相関性
が認められる。すなわち、接着力が大きいときには、
ｔｏも大きくなる傾向がある。また、（２）θ−１”ｂ
（ｒａ−ｒＬ）（’ ：液体の接触角、ｈ：液体の表
面張力、ｂ：定数）の関係が成立するので、γ０ が大
きければ、（２）−も大となり、すなわち、Ｉは小とな
りぬれ性も良好となる。The concept of critical surface strength (RO) proposed in Vol. There is a correlation between and 10. In other words, when the adhesive force is large,
to also tends to increase. Also, (2) θ−1”b
The relationship (ra-rL) (': contact angle of liquid, h: surface tension of liquid, b: constant) holds, so if γ0 is large, (2) - will also be large, that is, I will be small. The wettability is also improved.
ハロゲン、とくにフッ素を含有するアクリル酸エステル
高分子は、一般にｒＯがｌθ〜２５ ｄｙｎ・／ｃｌｌ
と極めて小ざい。この値は、′＄ジ型レジスト材料とし
て広く用いられているポリメチル°メタクリレー） （
ＰＭＭＡ ）のｒ。（約３６ ｄｙＨ／ａｍ ）−こ比
べても非常に小さい０
このことが、上記したノ１０ゲン含有アクリル酸エステ
ル誘導体のレジスト材料が基板との密着性及び親水性に
詔いて劣る原因であると考えられる。Acrylic acid ester polymers containing halogen, especially fluorine, generally have an rO of lθ~25 dyn/cll.
It's extremely small. This value is based on polymethyl methacrylate, which is widely used as a di-type resist material.
PMMA) r. (approximately 36 dyH/am) - This is extremely small compared to 0. This is believed to be the reason why the above-mentioned resist material of the acrylic acid ester derivative containing No. Conceivable.
本発明者らは、ハロゲン含有アクリル酸エステル誘導体
の密着性及び親水性を放勢すべく鋭意研究を重ねた結果
、本発明のレジスト材料を完成するに到った０
本発明は、高感度、高解儂性であって基板との密着性に
すぐれ、微細な回路／ずターンの形成６ご用いて有効な
ポジ型放射線感応レジスト材料の提供を目的とする０
本発明のレジスト材料は１
次式：
（式中、Ｘは塩素、シュウ素、フッ素のいずれかを表わ
し、Ｒは少くとも１個の水素原子がフッ素で置換された
炭素数１〜１０のアルキル基を表わし、ｍ、ｎはモル繁
であってそれぞれ、５０≦ｍ≦９９．５．０．５≦ｎ≦
５０の範囲で選ばれる。）で示される組成の共重合体で
あることを特徴とするＯ
本発明のレジスト材料としては、例えば、トリフルオロ
エチル−α−クロルアクリレート／α−クロルアクリル
酸共重合体、ジフルオロプロピル−ａ−クロルアクリレ
ート／α−クロルアクリル酸共重合体、テトラフルオロ
プロピル−α−クロルアクリレート／α−クロルアクリ
ル酸共重合体、オクトフルオロペンチル−α−ブロモア
クリレート／ａ−ブロモアクリル酸共重合体、トリフル
オロイソプロピル−α−フルオロアクリレート／α−フ
ルオロアクリル酸共重合体、トリフルオロ−ｔ−ブチル
−α−り、クルアクリレート／α−クロルアクリル酸共
重合体、トリフルオロイソプロピル−α−クロルアクリ
レート／ａ−クロルアクリル酸共重合体などを好ましい
ものとしてあげることができる０
本発明のレジスト材料は、各種のハロゲン含有アクリル
酸エステルを塩基性触媒（例えば、有機アミン類）を用
いて加水分解する方法、又は、各単量体（七ツマ−）を
常法に従って共重合する方法によって容易に合成するこ
とができる。The present inventors have conducted extensive research to improve the adhesion and hydrophilicity of halogen-containing acrylic acid ester derivatives, and as a result have completed the resist material of the present invention. It is an object of the present invention to provide a positive radiation-sensitive resist material which has high solubility, excellent adhesion to a substrate, and is effective for forming fine circuits/turns.The resist material of the present invention has a linear formula: (wherein, and 50≦m≦99.5.0.5≦n≦, respectively.
Selected from a range of 50. ) The resist material of the present invention is, for example, trifluoroethyl-α-chloroacrylate/α-chloroacrylic acid copolymer, difluoropropyl-a- Chloracrylate/α-chloroacrylic acid copolymer, tetrafluoropropyl-α-chloroacrylate/α-chloroacrylic acid copolymer, octofluoropentyl-α-bromoacrylate/a-bromoacrylic acid copolymer, trifluoro Isopropyl-α-fluoroacrylate/α-fluoroacrylic acid copolymer, trifluoro-t-butyl-α-di, chloracrylate/α-chloroacrylic acid copolymer, trifluoroisopropyl-α-chloroacrylate/a- Preferred examples include chloroacrylic acid copolymers. The resist material of the present invention can be prepared by a method in which various halogen-containing acrylic esters are hydrolyzed using a basic catalyst (for example, organic amines), or can be easily synthesized by copolymerizing each monomer (septumer) according to a conventional method.
このとき、ハロゲン含有アクリル酸エステルとハロゲン
ｔＶアクリル酸の共重合体におけるそれぞれの組成比（
ｍとｎ）は、モル繁で表わして５０≦ｍ≦９９．５．０
．５≦ｎ≦５０の範囲を満足するように選択される。レ
ジスト使用における溶剤への溶解性及び基板との密着性
という点からすると、ｍ、ｎはそれぞれ８０≦ｍ≦９９
．５．０．５≦ｎ≦２０を満足するモル％であることが
好ましい。At this time, the respective composition ratios (
m and n) are 50≦m≦99.5.0 expressed in molar numbers.
．． It is selected to satisfy the range of 5≦n≦50. In terms of solubility in solvents and adhesion to substrates when using a resist, m and n are each 80≦m≦99.
．． It is preferable that the mole % satisfies 5.0.5≦n≦20.
本発明のレジスト材料を用いた微細回路パターンの形成
は例えば次のようにして行なわれる。Formation of a fine circuit pattern using the resist material of the present invention is performed, for example, as follows.
まず、本発明のレジスト材料をメチルセロソルブアセテ
ート、エチルセロソルブアセテート、メチルセロソルブ
などの溶媒に溶解して塗布溶液とする。ついで、塗布溶
液をマスク基板又は苧導体基材にスピンコード法で厚み
０．２〜２μｍ塗布して【／シスト層とする。その後、
１５０〜２００℃の湯皺でプリベーク処理を施し残存す
る溶媒を除去する。First, the resist material of the present invention is dissolved in a solvent such as methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, or the like to prepare a coating solution. Next, the coating solution is coated onto a mask substrate or a conductor base material to a thickness of 0.2 to 2 μm using a spin code method to form a cyst layer. after that,
A prebaking treatment is performed in a hot water bath at 150 to 200°C to remove the remaining solvent.
ついで、このレジスト層に外部から制御された電子ビー
ム等の放射線を照射してパターンを描画し潜像を形成す
る◇その後、適当な溶媒で現儂処理し、描画部分を選択
的ｌこ除去して所望のポジ湿レジストパターンを形成す
る。引き続き、このレジストパターンを保＠膜として、
下地基板であるマスク材や牛導体基材に浸酸又は乾式の
エツチング処理を施して、上記レジストパターンに対応
する微細な回路パターンを形成する。Next, this resist layer is irradiated with externally controlled radiation such as an electron beam to draw a pattern and form a latent image. ◇Then, the resist layer is treated with an appropriate solvent to selectively remove the drawn portions. to form the desired positive wet resist pattern. Next, use this resist pattern as a protective film.
A fine circuit pattern corresponding to the resist pattern is formed by subjecting the mask material and conductor base material, which are the underlying substrates, to acid immersion or dry etching treatment.
以下に、本発明のレジスト材料の効果を実施例として示
す〇
実施例
トリフルオロエチル−α−クロルアクリレート／ａ−ク
ロルアクリル酸共重合体（ｍ：ｍ−８０＝２０）をメチ
ルセロソルブアセテートに溶解してレジスト塗布液とし
た。The effects of the resist material of the present invention are shown below as examples. Example Trifluoroethyl-α-chloroacrylate/a-chloroacrylic acid copolymer (m:m-80=20) was dissolved in methyl cellosolve acetate. A resist coating solution was prepared.
ガラス板に厚み１００ＯＡのクロム／酸化クロム層を設
けて成るフォトマスク基板の上に、上記塗布液をスピン
コード法で塗布し、厚み約５００ＯＡのレジスト膜を形
成した。これを、１７０℃で４０分間！リペーク処理し
、試料ｌとした。The above coating solution was applied by a spin code method onto a photomask substrate consisting of a glass plate provided with a chromium/chromium oxide layer with a thickness of 100 OA to form a resist film with a thickness of about 500 OA. Do this for 40 minutes at 170℃! It was subjected to re-processing and designated as sample 1.
比較のために、上記と同様のフォトマスク基板の上に、
Ｉリメチルメ！タリレート及び／Ｉノトリフルオーエチ
ルーーーり膓ルアクリレートのレノスト膜を形成した試
料を作成し、それぞれ試料２、試料３とし友。For comparison, on the same photomask substrate as above,
I remethyl me! Samples on which Renost films of talylate and /I-notrifluoroethyl-renost acrylate were formed were prepared and designated as Sample 2 and Sample 3, respectively.
これらの試料に、加速電圧２０ｋＶで電子ビームを照射
してノｆメーン状に描画し、メチルイノノチルケトンー
イノグロビルアルコール混合溶液で現像処理し４ジレノ
ヌトｄターンを形成し九。その後、レジヌト／譬！−ン
寸法をレーデ反射層寸法測定装置を用いて測定した。These samples were irradiated with an electron beam at an accelerating voltage of 20 kV to draw a nof main shape, and developed with a mixed solution of methylinonotylketone-inoglobil alcohol to form 4 direnonuto d-turns.9. After that, Resinut/Parable! The -n dimensions were measured using a Rede reflective layer dimension measuring device.
つぎに、下地基板であるり■ム層を硝酸セリウムアン４
二りム／過塩素酸を主成分とする酸性エツチング液で加
工処理してマスク／々ターンを形成し、上記と同様にそ
の寸法測定を行なつ九。Next, the underlying substrate, the rim layer, was coated with cerium nitrate anhydride 4.
A mask/turn is formed by processing with an acidic etching liquid mainly composed of two rims/perchloric acid, and its dimensions are measured in the same manner as above.
得られた結果を一括し、て表に示した。The obtained results are summarized and shown in the table.
表から明らかなように、本発明のレジスト材料は、試料
２の従来市販されているレジスト材料（ポリメチルメタ
クリレート）よりも一層高感度であり、解像度もほぼ同
様である０また、ハロゲン含有アクリル酸エステルの単
独重合体（試料３）ともほぼ同様の優れた値を示すが、
パターン変換差の値が示すように下地基板との密着性及
びエツチング均一性に関しては一層すぐれた特性を示し
ている。As is clear from the table, the resist material of the present invention has higher sensitivity than the conventional commercially available resist material (polymethyl methacrylate) of sample 2, and has almost the same resolution. It shows almost the same excellent value as the ester homopolymer (sample 3), but
As shown by the value of the pattern conversion difference, it exhibits better properties in terms of adhesion to the underlying substrate and etching uniformity.
このように、本発明のレジスト材料は高′＃！度で微細
な回路パターンの形成において、従来から知られている
レジスト材料に比べ極めて優れた特性を有するのでその
工業的価値は大である。In this way, the resist material of the present invention has a high '#! It has extremely superior properties compared to conventionally known resist materials in forming fine circuit patterns at high temperatures, so its industrial value is great.
Claims (1)
し、Ｒは少くとも１個の水素原子がフッ１Ａで置換され
た炭素数１〜１０のアルキル基を表わしｓ ｍ ＠ ｎ
Ｇ’；１モル％であって、それぞれ５０≦ｍ≦９９．
５．０．５≦ｎ≦５０の範囲で選ばれる０） で示されるポジ製放射線感応レジスト材料。 ２、ｒｎ、ｍがそれぞれ８０≦ｍ≦９９．５．０．５≦
ｎ≦２０の範囲である特許請求の範囲第１項記載のポジ
型放射線感応レジスト材料。[Claims] 1. The following formula 5: (wherein, Represents an alkyl group of 1 to 10, s m @ n
G': 1 mol%, each 50≦m≦99.
5. A positive radiation-sensitive resist material selected from the range of 0.5≦n≦50. 2, rn, m are each 80≦m≦99.5.0.5≦
The positive radiation-sensitive resist material according to claim 1, wherein n≦20.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15820481A JPS5859443A (en) | 1981-10-06 | 1981-10-06 | Positive type radiation-sensitive resist material |
| EP82109234A EP0076524A1 (en) | 1981-10-06 | 1982-10-06 | Radiation-sensitive positive resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15820481A JPS5859443A (en) | 1981-10-06 | 1981-10-06 | Positive type radiation-sensitive resist material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5859443A true JPS5859443A (en) | 1983-04-08 |
Family
ID=15666551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15820481A Pending JPS5859443A (en) | 1981-10-06 | 1981-10-06 | Positive type radiation-sensitive resist material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5859443A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60117243A (en) * | 1983-11-30 | 1985-06-24 | Fujitsu Ltd | Formation pattern |
| KR100767938B1 (en) | 2002-12-11 | 2007-10-18 | 삼성전자주식회사 | Composition for forming a conjugated polymer pattern and Process of Pattern Formation using the same |
-
1981
- 1981-10-06 JP JP15820481A patent/JPS5859443A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60117243A (en) * | 1983-11-30 | 1985-06-24 | Fujitsu Ltd | Formation pattern |
| JPH052980B2 (en) * | 1983-11-30 | 1993-01-13 | Fujitsu Ltd | |
| KR100767938B1 (en) | 2002-12-11 | 2007-10-18 | 삼성전자주식회사 | Composition for forming a conjugated polymer pattern and Process of Pattern Formation using the same |
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