JPH03148659A - Ionizing radiation sensitive negative type resist material composition - Google Patents
Ionizing radiation sensitive negative type resist material compositionInfo
- Publication number
- JPH03148659A JPH03148659A JP1287444A JP28744489A JPH03148659A JP H03148659 A JPH03148659 A JP H03148659A JP 1287444 A JP1287444 A JP 1287444A JP 28744489 A JP28744489 A JP 28744489A JP H03148659 A JPH03148659 A JP H03148659A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ionizing radiation
- alkyl group
- polymer
- molecular weight
- 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
- 230000005865 ionizing radiation Effects 0.000 title claims description 14
- 239000000463 material Substances 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 19
- 238000001312 dry etching Methods 0.000 abstract description 6
- -1 12C alkyl halide Chemical class 0.000 abstract description 3
- 150000001348 alkyl chlorides Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- HXLLCROMVONRRO-UHFFFAOYSA-N 2-butoxyethenylbenzene Chemical group CCCCOC=CC1=CC=CC=C1 HXLLCROMVONRRO-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001091433 Itea Species 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006180 TBST buffer Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Landscapes
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔概 要〕
電離放射線感応性ネガ型レジスト材料に関し、解像性、
感度およびドライエッチング耐性の高い電離放射線感応
性ネガ型レジスト材料を提供することを目的とし、
悉
■
１＊ ＣＲｚ
れ
（式中、Ｒ１はハロゲン、または炭素数１〜１２のモノ
もしくはポリハロゲン化アルキル基を表わし、Ｒｔ、Ｒ
ｓは、それぞれ水素、ハロゲン、または炭素数１−１２
のモノもしくはポリハロゲン化アルキル基を表わし、Ｒ
，，Ｒ，は、それぞれ水素、または炭素数１〜３のアル
キル基を表わし、Ｒ，は水素、または炭素数１〜１２の
アルキル基を表わし、Ｒａ、Ｒｖは、それぞれ炭素数１
−１２のアルキル基を表わす）で示される繰り返し単位
を含み、その全数に対して式（１）の繰り返し単位の数
が１０〜８５％、式（２）の繰り返し単位の数が１５〜
９０％であり、かつ重量平均分子量が２．０００〜１．
０００，０００であるように構成する。[Detailed Description of the Invention] [Summary] Regarding a negative resist material sensitive to ionizing radiation,
The purpose is to provide a negative resist material sensitive to ionizing radiation with high sensitivity and dry etching resistance. represents a group, Rt, R
s is hydrogen, halogen, or carbon number 1-12, respectively
represents a mono- or polyhalogenated alkyl group, R
,,R, each represent hydrogen or an alkyl group having 1 to 3 carbon atoms, R represents hydrogen or an alkyl group having 1 to 12 carbon atoms, and Ra and Rv each represent an alkyl group having 1 to 3 carbon atoms.
-12 representing an alkyl group), the number of repeating units of formula (1) is 10 to 85% of the total number, and the number of repeating units of formula (2) is 15 to 85% of the total number.
90%, and the weight average molecular weight is 2.000 to 1.
000,000.
本発明は電離放射線感応性ネガ型レジスト材料組成物に
関する。The present invention relates to a negative resist material composition sensitive to ionizing radiation.
近年、半導体装置などの高集積化にともない、配線はま
すます微細化されている。最新６４ＰＩｂｉ ｔのＤ−
ＲＡＩＩの最小線幅は０．７ｎ程度で、今後さらに配線
は細くなる傾向にある。それに伴い、レジスト材料もこ
のような微細な配線パターンの解像ができる高解像性の
ものが望まれており、また生産量をあげるために高感度
のものが必要とされている。In recent years, as semiconductor devices and the like have become highly integrated, wiring has become increasingly finer. Latest 64PIbit D-
The minimum line width of RAII is about 0.7n, and there is a tendency for interconnections to become even thinner in the future. Accordingly, resist materials with high resolution that can resolve such fine wiring patterns are desired, and resist materials with high sensitivity are also required to increase production volume.
また、レジストとしてはドライエッチング耐性に優れて
いることも重要な条件である。Another important condition is that the resist has excellent dry etching resistance.
ドライエッチング耐性の優れたものとして、特にポリス
チレン系のものが知られているが、ポリスチレンはそれ
自体電離放射線に対して非常に感度が低く、そのままで
はレジストとしては用いられない、そこで不飽和基など
の反応性の高い基を導入して感度を向上させるという方
法が採られている。しかし、その感度が電離放射線によ
って起こる架橋反応のみに依存しているので、一般に低
感度である場合が多い、さらに感度を上げるために不飽
和基を増やすと、未露光部にまで架橋反応が起こってコ
ントラストを低下させ、かえって解像性を低くする場合
もある。Polystyrene-based materials are particularly known as having excellent dry etching resistance, but polystyrene itself has very low sensitivity to ionizing radiation and cannot be used as a resist as it is. A method has been adopted to improve sensitivity by introducing highly reactive groups. However, since its sensitivity depends only on the crosslinking reaction caused by ionizing radiation, the sensitivity is generally low.If the number of unsaturated groups is increased to further increase the sensitivity, the crosslinking reaction will occur even in the unexposed areas. In some cases, the contrast may be lowered and the resolution may be lowered.
また、解像性の高いものとして、一般に化学増幅系レジ
ストと呼ばれるものが知られている。これは、レジスト
に酸発生剤を含むものてあって、電離放射線を照射して
、酸を発生させ、発生した酸が触媒的に作用して、ポリ
マーを架橋または分解するものである。これはポリマー
に酸発生剤を加える必要がある。Furthermore, as a resist with high resolution, what is generally called a chemically amplified resist is known. In this method, the resist contains an acid generator, and ionizing radiation is irradiated to generate acid, and the generated acid acts catalytically to crosslink or decompose the polymer. This requires adding an acid generator to the polymer.
（発明の解決すべき課題〕
本発明は、従来のレジストとは異なって、反応性の高い
官能基を導入することもなく、また、酸発生剤を加えず
にポリマ一分子自身が酸発生剤に対応する部分を含み、
これが酸を発生して架橋反応を起こし、高感度化を達成
し、かつ解像性に優れたドライエッチング耐性も高い電
離散線感応性ネガ型レジストを従供することを目的とす
る。(Problems to be Solved by the Invention) Unlike conventional resists, the present invention does not introduce highly reactive functional groups, and does not require the addition of an acid generator. including a portion corresponding to
This generates acid to cause a crosslinking reaction, and the object is to provide an ionized radiation-sensitive negative resist that achieves high sensitivity, has excellent resolution, and has high dry etching resistance.
本発明の上記課題は、
れ
（式中、Ｒ１はハロゲン、または炭素数１〜１２のモノ
もしくはポリハロゲン化アルキル基を表わし、Ｒｔ、Ｒ
ｓは、それぞれ水素、ハロゲン、または炭素数１−１２
のモノもしくはポリハロゲン化アルキル基を表わし、Ｒ
４，Ｒ＠は、それぞれ水素、または炭素数１〜３のアル
キル基を表わし、Ｒｓは水素、または度素数１〜１２の
アルキル基を表わし、Ｒ，，Ｒ，は、、それぞれ炭素数
１〜１２のアルキル基を表わす）で示される繰り返し単
位を含み、その全数に対して式（１）の繰り返し単位の
数が１０〜８５％、式（２）の繰り返し単位の数が１５
〜９０％であり、かつ重量平均分子量が２．０００〜ｔ
、ｏｏｏ、ｏｏ。The above-mentioned problem of the present invention is to solve the following problems:
s is hydrogen, halogen, or carbon number 1-12, respectively
represents a mono- or polyhalogenated alkyl group, R
4, R@ each represents hydrogen or an alkyl group having 1 to 3 carbon atoms, Rs represents hydrogen or an alkyl group having 1 to 12 carbon atoms, and R,,R, each represents an alkyl group having 1 to 3 carbon atoms. (representing an alkyl group of 12), the number of repeating units of formula (1) is 10 to 85% of the total number, and the number of repeating units of formula (2) is 15%
~90%, and the weight average molecular weight is 2.000~t
,ooo,oo.
であるレジストによって達成することができる。This can be achieved with a resist that is
レジストに電離放射線を照射するとポリマー同士で架橋
反応が起こり、分子量が増大して現像液に不溶化するが
、分子量が最初から大きいと、少しの架橋反応で分子量
が不溶化に充分な値に達する。従って分子量が高いほど
電離放射線の照射量が少なくて済む、即ち感度が高いこ
とになる。しかし分子量が高いと現像液に浸した際に膨
潤という現象が起こる。これはレジストでパターンを作
成した際にそのパターンが現像液を吸って膨らむ現象で
、甚だしい場合にはそれぞれのパターンがくっついてし
まう場合もあり、解像性を低下させる重要な原因とされ
ている。ポリマーの分子量が高いはど膨潤も大きくなる
ので、レジストに使用するポリマーの分子量には感度と
解像性の点から最適値が存在する。When a resist is irradiated with ionizing radiation, a crosslinking reaction occurs between the polymers, increasing their molecular weight and making them insolubilized in a developing solution.However, if the molecular weight is large from the beginning, a small amount of crosslinking reaction will reach a value sufficient for insolubilization. Therefore, the higher the molecular weight, the smaller the amount of ionizing radiation required, that is, the higher the sensitivity. However, if the molecular weight is high, a phenomenon called swelling occurs when immersed in a developer. This is a phenomenon in which when a pattern is created with resist, the pattern absorbs the developer and swells. In extreme cases, the patterns may stick together, and is considered to be an important cause of reduced resolution. . The higher the molecular weight of the polymer, the greater the swelling, so there is an optimum value for the molecular weight of the polymer used in the resist from the viewpoint of sensitivity and resolution.
本発明のポリマーは重量平均分子量が１．０００．００
０を超えると、解像性が低下し、２．０００未満では電
離放射線感度が低下する。The polymer of the present invention has a weight average molecular weight of 1.000.00
If it exceeds 0, the resolution will decrease, and if it is less than 2.000, the sensitivity to ionizing radiation will decrease.
本発明のポリマーは、式（１）で示される繰り返し単位
のＲｔ 、 ＲｔまたはＲ３に含まれるハロゲンが、電
離放射線の照射によってはずれてラジカルとなり、はず
れた部分において相互に架橋して高分子量化する。これ
によって照射された領域は、有機溶媒に対する溶解度が
減少するので、現像されてパターンを形成する。In the polymer of the present invention, the halogen contained in Rt, Rt, or R3 of the repeating unit represented by formula (1) is detached by irradiation with ionizing radiation and becomes a radical, and the detached portions are crosslinked with each other and have a high molecular weight. . The irradiated areas are thereby developed to form a pattern as their solubility in organic solvents is reduced.
さらに、注目すべきことは、このとき発生したハロゲン
ラジカルが、レジスト中に残存する有機溶媒から水素を
引き抜いてハロゲン化水素になる。Furthermore, it should be noted that the halogen radicals generated at this time extract hydrogen from the organic solvent remaining in the resist and become hydrogen halides.
こうして生成したハロゲン化水素は、繰り返し単位（２
）の中のターシャルブトキシ基を攻撃する。The hydrogen halide thus generated is a repeating unit (2
) attacks the tertiary butoxy group in
このためターシャルブトキシ基は下式のように、はずれ
、水酸基となる。Therefore, the tertiary butoxy group is dislocated and becomes a hydroxyl group, as shown in the formula below.
れ
こうして、ポリマーの極性が変化し、無極性溶媒に対す
る溶解度がますます低下する。即ち本発明になるポリマ
ーは、感度が架橋反応のみならず同時に発生するハロゲ
ン化水素による加水分解に起因するポリマー自身の極性
の変化にも依存していることが大きな特徴である。また
このハロゲン化水素は触媒的に使用されるため、１分子
のハロゲン化水素が多くのターシャルブトキシ基を攻撃
することが可能である。As a result, the polarity of the polymer changes, making it increasingly less soluble in non-polar solvents. That is, a major feature of the polymer of the present invention is that its sensitivity depends not only on the crosslinking reaction but also on the change in polarity of the polymer itself caused by hydrolysis by hydrogen halide that occurs simultaneously. Moreover, since this hydrogen halide is used catalytically, one molecule of hydrogen halide can attack many tertiary butoxy groups.
従って、ポリマー中の繰り返し単位の全数に対して、繰
り返し単位（１）の数が、ｌＯ％未満では発生するハロ
ゲンラジカルの量が不足し、８５％を超えると、ハロゲ
ンが遊離して大量のハロゲン化水素を発生しても、繰り
返し単位（２）の数が少ないので加水分解されるアルコ
キシ基が少ないため、電離放射線照射前後のポリマーの
極性の変化が小さくなり単に架橋反応にのみ感度が依存
してしまうことになる。従って感度は大して上がらず、
既存のレジスト材料となんら遅いがなくなる。Therefore, if the number of repeating units (1) is less than 10% of the total number of repeating units in the polymer, the amount of halogen radicals generated will be insufficient, and if it exceeds 85%, halogens will be liberated and a large amount of halogen radicals will be generated. Even if hydrogen hydride is generated, there are fewer alkoxy groups to be hydrolyzed due to the small number of repeating units (2), so the change in polarity of the polymer before and after irradiation with ionizing radiation is small, and the sensitivity depends solely on the crosslinking reaction. This will result in Therefore, the sensitivity does not increase much,
No slowness compared to existing resist materials.
繰り返し単位（１）中のＲ１〜Ｒ３の炭素数が１２より
多い場合、一方においてモノマの分子量が太き（なり、
他方においてポリマーの分子量に上限があるので、重合
したポリマー中の繰り返し単位（１）の数を所望のｌＯ
％より少なくする必要がおき、また炭素鎖が長ずざるの
で、立体障害によって重合が困難となり、ポリマーの分
子量が２．０００未満になることがおきる。When the number of carbon atoms in R1 to R3 in the repeating unit (1) is more than 12, on the other hand, the molecular weight of the monomer is thick (
On the other hand, since there is an upper limit to the molecular weight of the polymer, the number of repeating units (1) in the polymerized polymer can be adjusted to the desired lO
%, and since the carbon chain is not long, polymerization becomes difficult due to steric hindrance, and the molecular weight of the polymer may become less than 2.000.
繰り返し単位（２）中のＲ，〜Ｒｔの炭素数が１２より
多い場合も、上記と同じ欠点を生じ、さらに、立体障害
によってアルコキシ基の酸素原子がブロックされて加水
分解が困難となる。If the number of carbon atoms in R, .
また、Ｒａ、Ｒｍの炭素数が３より多いと、立体障害の
原因となり、またこれらの炭素数を３以下に限定するこ
とによって、Ｒ１〜Ｒ，およびＲＳ〜Ｒ７の炭素数を１
２までと多くすることができる。Furthermore, if the number of carbon atoms in Ra and Rm is more than 3, it causes steric hindrance, and by limiting the number of carbon atoms in these to 3 or less, the number of carbon atoms in R1 to R and RS to R7 can be reduced to 1.
It can be as many as 2.
（合成例１）
アリルクロライド７．９ｇ （０，１＠ｏｊ！）と、Ｐ
ＴＢＳＴ（パラターシャルブトキシスチレン、北興化学
工業）１７ｇ （０，１ｓｏｊ！）を、水素化カルシラ
ムチ充分乾燥後さらに金属ナトリウム存在下で蒸留した
ＴＨＦＩＧＯ−に混合し、精製窒素気流下で、これに重
合開始剤としてノルマルブチルリチウム１ｇを加え、−
７８℃で３時間反応させた。その後反応溶液を大量のメ
タノール中に注ぎ、アリルクロライドとＰＴＢＳＴの共
重合体を析出させた。こうして得られたポリマー２ｇを
、さらにベンゼン−メタノールで５ｇ精製した。その結
果、最終的に得られたポリマーの重量平均分子量は１、
５ ＸＩＯ、分散度は１．１２、収率は９５．０％であ
った。元素分析の結果によると、このポリマ一分子中の
（１）式で表される繰り返し・単位と（２）式で表され
る繰り返し単位の比は、はぼｌ：１であった。(Synthesis Example 1) 7.9 g of allyl chloride (0,1@oj!) and P
17 g (0.1 soj!) of TBST (paratertiary butoxystyrene, Hokko Chemical Industry) was mixed with THFIGO- which had been thoroughly dried with hydrogenated calciramthi and further distilled in the presence of metallic sodium, and polymerized therein under a stream of purified nitrogen. Add 1 g of n-butyllithium as an initiator, -
The reaction was carried out at 78°C for 3 hours. Thereafter, the reaction solution was poured into a large amount of methanol to precipitate a copolymer of allyl chloride and PTBST. 2 g of the polymer thus obtained was further purified with 5 g of benzene-methanol. As a result, the weight average molecular weight of the finally obtained polymer was 1,
5XIO, the dispersity was 1.12, and the yield was 95.0%. According to the results of elemental analysis, the ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) in one molecule of this polymer was approximately 1:1.
（合成例２）
３．４−ジクロロ−２−メチル−１−ブテン１４．２ｇ
（０，１ｍｏｊ！）と、ＰＴＢＳＴ （北興化学工業）
１７ｇ（０，，ｌｓｏｆｆｉ）を、（合成例１）と全く
同じように共重合させた。その結果、最終的に得られた
ポリマーの重量平均分子量は２．７ＸｌＯ、分散度は１
．０７、収率は９２．５％であった。また、このポリマ
一分子中の（１）式で表される繰り返し単位と（２）式
で表される繰り返し単位の比は、やはりほぼ１；Ｉであ
った。(Synthesis Example 2) 14.2 g of 3.4-dichloro-2-methyl-1-butene
(0.1 moj!) and PTBST (Hokuko Chemical Industry)
17 g (0,,lsoffi) was copolymerized in exactly the same manner as in (Synthesis Example 1). As a result, the weight average molecular weight of the finally obtained polymer was 2.7XlO, and the degree of dispersion was 1.
．． 07, yield was 92.5%. Moreover, the ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) in one molecule of this polymer was also approximately 1:I.
（実施例１）
（合成例１）により得られたポリマー１ｇをＭＩＢＫ（
メチルイソブチルケトン）５ｇに溶解してレジスト溶液
を作り、スピンコードによりシリコンウェハにＩＩＩ厚
がＩｔｅａになるように塗布し、８０℃で２０分間プリ
ベークし、電子線を照射し、ｌｌｌＢＫで３０秒間現像
し、ＩＰＡ（イソプロパノール）で３０秒間洗浄した。(Example 1) 1 g of the polymer obtained in (Synthesis Example 1) was mixed with MIBK (
Prepare a resist solution by dissolving 5 g of methyl isobutyl ketone), apply it to a silicon wafer using a spin code so that the thickness is III to Itea, prebake at 80°C for 20 minutes, irradiate with an electron beam, and develop with IllBK for 30 seconds. and washed with IPA (isopropanol) for 30 seconds.
このようにして電子線感度を測定したところ残膜率９０
％のところで２１＃Ｃ／ａｉであった。また最小０．３
μのパターンを解像する二ｔができた。When the electron beam sensitivity was measured in this way, the residual film rate was 90.
% was 21#C/ai. Also minimum 0.3
We have created a 2t that can resolve the μ pattern.
またＸ線マスク（大日本印刷、ミクロ製品研究所製）を
介してＰｄＬａ線（４，３７人）を４５ｓＪ／ａｉの露
光量で照射した。このようにして得られたパターンを走
査型電子顕微鏡で観察したところ、０．４ ｔｍのライ
ンアンドスペースを解像できた。In addition, PdLa rays (4,37 people) were irradiated with an exposure dose of 45 sJ/ai through an X-ray mask (manufactured by Dainippon Printing, Micro Product Research Institute). When the pattern thus obtained was observed with a scanning electron microscope, lines and spaces of 0.4 tm could be resolved.
（実施例２）
（実施例１）と同様にして（合成例２）で作製したポリ
マーの電子線感度を測定したところｔｓｇｃ／ｄで、最
小０．３ Ｊｌｌｌのラインパターンが解像できた。Ｘ
線感度は４０ｓ＋Ｊ／ｄだった。(Example 2) When the electron beam sensitivity of the polymer produced in (Synthesis Example 2) was measured in the same manner as in (Example 1), a line pattern of a minimum of 0.3 Jlll could be resolved at tsgc/d. X
Line sensitivity was 40s+J/d.
本発明によれば、感度、解像性ともに優れ、またドライ
エッチング耐性も高い電離放射線感応性ネガ型レジスト
を捷供できる。According to the present invention, an ionizing radiation-sensitive negative resist having excellent sensitivity and resolution and high dry etching resistance can be provided.
Claims (1)
ノもしくはポリハロゲン化アルキル基を表わし、Ｒ＿２
、Ｒ＿３は、それぞれ水素、ハロゲン、または炭素数１
〜１２のモノもしくはポリハロゲン化アルキル基を表わ
し、Ｒ＿４、Ｒ＿８は、それぞれ水素、または炭素数１
〜３のアルキル基を表わし、Ｒ＿５は水素、または炭素
数１〜１２のアルキル基を表わし、Ｒ＿６、Ｒ＿７は、
それぞれ炭素数１〜１２のアルキル基を表わす）で示さ
れる繰り返し単位を含み、その全数に対して式（１）の
繰り返し単位の数が１０〜８５％、式（２）の繰り返し
単位の数が１５〜９０％であり、かつ重量平均分子量が
２、０００〜１、０００、０００である共重合体を含む
、ことを特徴とする、電離放射線感応性ネガ型レジスト
材料組成物。[Claims] Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is halogen or a monomer having 1 to 12 carbon atoms. or represents a polyhalogenated alkyl group, R_2
, R_3 are each hydrogen, halogen, or carbon number 1
~12 mono- or polyhalogenated alkyl groups, R_4 and R_8 are each hydrogen or a carbon number of 1
~3 alkyl group, R_5 represents hydrogen or an alkyl group having 1 to 12 carbon atoms, R_6 and R_7 are
each representing an alkyl group having 1 to 12 carbon atoms), the number of repeating units of formula (1) is 10 to 85% of the total number, and the number of repeating units of formula (2) is 10 to 85% of the total number. An ionizing radiation-sensitive negative resist material composition, comprising a copolymer having a weight average molecular weight of 15 to 90% and a weight average molecular weight of 2,000 to 1,000,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1287444A JPH03148659A (en) | 1989-11-06 | 1989-11-06 | Ionizing radiation sensitive negative type resist material composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1287444A JPH03148659A (en) | 1989-11-06 | 1989-11-06 | Ionizing radiation sensitive negative type resist material composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03148659A true JPH03148659A (en) | 1991-06-25 |
Family
ID=17717404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1287444A Pending JPH03148659A (en) | 1989-11-06 | 1989-11-06 | Ionizing radiation sensitive negative type resist material composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03148659A (en) |
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|---|---|---|---|---|
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-
1989
- 1989-11-06 JP JP1287444A patent/JPH03148659A/en active Pending
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