JPH11124531A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JPH11124531A JPH11124531A JP29205197A JP29205197A JPH11124531A JP H11124531 A JPH11124531 A JP H11124531A JP 29205197 A JP29205197 A JP 29205197A JP 29205197 A JP29205197 A JP 29205197A JP H11124531 A JPH11124531 A JP H11124531A
- Authority
- JP
- Japan
- Prior art keywords
- unit represented
- fluorine
- formula
- photoresist
- coating composition
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体製造などに
おけるフォトレジストを用いたフォトリソグラフィの際
に使用する反射防止コーティング組成物などとして有用
なコーティング組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition useful as an antireflection coating composition for use in photolithography using a photoresist in semiconductor production or the like.
【０００２】[0002]
【従来の技術】フォトリソグラフィによってフォトレジ
ストのパターンを形成する際、露光時にフォトレジスト
層と基材との境界面およびフォトレジスト層表面におい
て光が反射することによる光の多重干渉はパターン寸法
精度を低下させる。これを防止する目的で、従来よりフ
ォトレジスト層表面に反射防止膜を形成する方法が検討
されている。反射防止膜としては、一般に以下の性能を
有するものが望ましいとされている。2. Description of the Related Art When a photoresist pattern is formed by photolithography, multiple interference of light due to reflection of light at the interface between the photoresist layer and the substrate and at the surface of the photoresist layer during exposure reduces the pattern dimensional accuracy. Lower. In order to prevent this, a method of forming an antireflection film on the surface of a photoresist layer has been conventionally studied. It is generally considered that an antireflection film having the following performance is desirable.
【０００３】（１）公知の反射防止理論により、反射防
止効果は反射防止膜の屈折率がフォトレジストの屈折率
の平方根に等しい場合に最大となるので、その値にでき
るだけ近いことが望ましい。具体的には、屈折率値が
１．４より小さい反射防止膜が切望されている。一般的
なフォトレジストの屈折率１．６〜１．８に対して、反
射防止膜の屈折率は１．２７〜１．３４が理想的であ
り、この値からのずれが大きくなるほど反射防止性能は
低下する。(1) According to the well-known antireflection theory, the antireflection effect is maximized when the refractive index of the antireflection film is equal to the square root of the refractive index of the photoresist. Specifically, an antireflection film having a refractive index value smaller than 1.4 has been desired. Ideally, the refractive index of the anti-reflection film is 1.27 to 1.34, whereas the refractive index of the general photoresist is 1.6 to 1.8. Drops.
【０００４】（２）反射防止膜の除去が、フォトレジス
トの現像液によって行われることが望ましい。露光後の
フォトレジストの現像は、テトラメチルアンモニウムヒ
ドロキシド水溶液などのアルカリ水溶液により行われる
が、この際に反射防止膜も同時に除去されることが、工
程短縮、歩留まり向上の観点より望ましい。(2) It is desirable that the removal of the antireflection film is performed by using a photoresist developer. The development of the photoresist after the exposure is performed with an alkaline aqueous solution such as an aqueous solution of tetramethylammonium hydroxide. At this time, it is preferable that the antireflection film be removed at the same time from the viewpoint of shortening the process and improving the yield.
【０００５】これまでに種々の反射防止膜が開示されて
いる（特開昭６２−６２５２１、特開平５−１８８５９
８、特開平６−１４８８９６、特開平８−３０５０３
２、特開平９−５０１２９、特開平９−９０６１５）
が、これら反射防止膜の屈折率は実用上１．４〜１．５
程度であり、理想的な屈折率値からのかい離が大きいた
め、充分な反射防止性能を発現できなかった。Various antireflection films have been disclosed (JP-A-62-62521, JP-A-5-18859).
8, JP-A-6-148896, JP-A-8-30503
2, JP-A-9-50129 and JP-A-9-90615)
However, the refractive index of these antireflection films is practically 1.4 to 1.5.
And the deviation from the ideal refractive index value was large, so that sufficient antireflection performance could not be exhibited.
【０００６】１．３〜１．３４という理想的な屈折率値
を有する反射防止膜も開示されている（特開昭６２−６
２５２０、特開平５−７４７００）が、これらはアルカ
リ水溶液に溶解しないため、フォトレジスト現像前に特
殊な溶剤にて膜を除去する必要があり、工程数の増加、
歩留まりの低下を招いていた。An antireflection film having an ideal refractive index value of 1.3 to 1.34 has also been disclosed (Japanese Patent Laid-Open No. 62-6 / 1987).
2520, JP-A-5-74700), since these do not dissolve in an alkaline aqueous solution, it is necessary to remove the film with a special solvent before developing the photoresist.
This has led to a decrease in yield.
【０００７】屈折率が１．４より小さく、アルカリ水溶
液にもある程度溶解する反射防止膜も開示されている
（特開平６−１８０１６８）が、アルカリ水溶液に対す
る飽和溶解量、溶解速度が充分ではないため、フォトレ
ジスト現像時に発生する微量の溶解残渣が歩留まり低下
の原因となり、実用化には至っていない。An antireflection film having a refractive index of less than 1.4 and dissolving to some extent in an alkaline aqueous solution is also disclosed (Japanese Patent Application Laid-Open No. 6-180168). However, a small amount of dissolved residue generated during the development of a photoresist causes a reduction in yield, and has not been put to practical use.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、アルカリ水
溶液に対する充分な溶解性と１．４より小さい屈折率値
とが両立する、フォトレジスト用反射防止コーティング
組成物などとして有用なコーティング組成物を提供する
ことを目的とする。SUMMARY OF THE INVENTION The present invention provides a coating composition useful as an antireflection coating composition for photoresists, which has both a sufficient solubility in an aqueous alkali solution and a refractive index value of less than 1.4. The purpose is to provide.
【０００９】[0009]
【課題を解決するための手段】本発明は、下記式１で表
される重合単位を含むフッ素系重合体または下記式１で
表される重合単位と下記式２で表される重合単位とを含
むフッ素系重合体を含有することを特徴とするコーティ
ング組成物である。ただし、式中、Ｒｆはエーテル性酸
素原子を含んでもよい直鎖状または分岐状のペルフルオ
ロアルキレン基、−ＣＯＯＭは−ＣＯＯＨ、−ＣＯＯＹ
（Ｙは置換されていてもよいアンモニウムイオン）、ま
たは−ＣＯＯＨ・Ｚ（Ｚはアミン）、Ｘはフッ素原子ま
たは塩素原子である。According to the present invention, there is provided a fluoropolymer containing a polymerized unit represented by the following formula (1) or a polymerized unit represented by the following formula (1) and a polymerized unit represented by the following formula (2): And a fluorine-containing polymer. However, in the formula, Rf is a linear or branched perfluoroalkylene group which may contain an etheric oxygen atom, and -COOM is -COOH, -COOY.
(Y is an optionally substituted ammonium ion) or —COOH · Z (Z is an amine), and X is a fluorine atom or a chlorine atom.
【００１０】[0010]
【化２】−ＣＦ2 ＣＦ（ＯＲｆＣＯＯＭ）− 式１ −ＣＦ2 ＣＦＸ− 式２Embedded image —CF 2 CF (ORfCOOM) —Formula 1 —CF 2 CFX—Formula 2
【００１１】本発明におけるフッ素系重合体は式１で表
される重合単位を含むフッ素系重合体または式１で表さ
れる重合単位と式２で表される重合単位とを含むフッ素
系重合体である。The fluoropolymer in the present invention is a fluoropolymer containing a polymer unit represented by the formula (1) or a fluoropolymer containing a polymer unit represented by the formula (1) and a polymer unit represented by the formula (2) It is.
【００１２】式１におけるＲｆはエーテル性酸素原子を
含んでもよい直鎖状または分岐状のペルフルオロアルキ
レン基である。ペルフルオロアルキレン基の炭素数は入
手の容易性などから１〜１０が好ましく、２〜７がより
好ましい。エーテル性酸素原子は通常ペルフルオロアル
キレン基の炭素間に存在するが、式１における−ＣＯＯ
Ｍの炭素とペルフルオロアルキレン基の炭素間に存在し
てもよい。Rf in Formula 1 is a linear or branched perfluoroalkylene group which may contain an etheric oxygen atom. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 10, and more preferably from 2 to 7 in terms of availability. The etheric oxygen atom is usually present between the carbons of the perfluoroalkylene group.
It may be present between the carbon of M and the carbon of the perfluoroalkylene group.
【００１３】−ＣＯＯＭは−ＣＯＯＨ、−ＣＯＯＹ（Ｙ
は置換されていてもよいアンモニウムイオン）、または
−ＣＯＯＨ・Ｚ（Ｚはアミン）である。式２におけるＸ
はフッ素原子または塩素原子である。-COOM is -COOH, -COOY (Y
Is an optionally substituted ammonium ion) or —COOH · Z (Z is an amine). X in Equation 2
Is a fluorine atom or a chlorine atom.
【００１４】前記Ｙの置換されていてもよいアンモニウ
ムイオンとしては、ＮＨ4 +およびＮＨ4 +の水素原子の１
以上をアルキル基、酸基、水酸基などの有機基で置換し
たものが挙げられる。The optionally substituted ammonium ion for Y includes NH 4 + and one of NH 4 + hydrogen atoms.
What substituted the above by organic groups, such as an alkyl group, an acid group, and a hydroxyl group, is mentioned.
【００１５】前記Ｚのアミンとしては、本発明の目的を
妨げないものであれば、公知周知の化合物の１種以上が
使用できる。例えば、エチルアミン、プロピルアミンな
どのモノアルキルアミン類、ジエチルアミンなどのジア
ルキルアミン類、トリエチルアミンなどのトリアルキル
アミン類、エタノールアミン、ジエタノールアミンなど
のアルカノールアミン類などが挙げられる。As the amine of Z, one or more known compounds can be used as long as they do not interfere with the object of the present invention. Examples include monoalkylamines such as ethylamine and propylamine, dialkylamines such as diethylamine, trialkylamines such as triethylamine, and alkanolamines such as ethanolamine and diethanolamine.
【００１６】フッ素系重合体は、式１で表される重合単
位のみからなる重合体、または、式１で表される重合単
位と式２で表される重合単位のみからなる重合体、が好
ましいが、式１で表される重合単位および式２で表され
る重合単位以外の重合単位を１０モル％以下で含む重合
体でもよい。The fluoropolymer is preferably a polymer composed of only the polymerized unit represented by the formula (1) or a polymer composed of only the polymerized unit represented by the formula (1) and the polymerized unit represented by the formula (2). May be a polymer containing 10 mol% or less of a polymer unit other than the polymer unit represented by the formula 1 and the polymer unit represented by the formula 2.
【００１７】式１で表される重合単位および式２で表さ
れる重合単位以外の重合単位としては、ペルフルオロビ
ニルエーテル類、炭素数３以上のペルフルオロオレフィ
ン類などの重合性ペルフルオロ化合物類に基づく重合単
位が挙げられる。Examples of the polymerized unit other than the polymerized unit represented by Formula 1 and the polymerized unit represented by Formula 2 include polymerized units based on polymerizable perfluoro compounds such as perfluorovinyl ethers and perfluoroolefins having 3 or more carbon atoms. Is mentioned.
【００１８】式１で表される重合単位と式２で表される
重合単位とを含むフッ素系重合体において、式１で表さ
れる重合単位および式２で表される重合単位の合計に対
する、式１で表される重合単位の割合は、４０モル％以
上で１００モル％未満が好ましく、５０モル％以上で１
００モル％未満がより好ましい。式１で表される重合単
位および式２で表される重合単位の合計に対する、式２
で表される重合単位の割合は、０モル％超６０モル％以
下が好ましく、０モル％超５０モル％以下がより好まし
い。式１で表される重合単位の割合を４０モル％以上と
することによりフッ素系重合体のアルカリ水溶液に対す
る溶解性が向上する。In a fluorine-containing polymer containing a polymerized unit represented by the formula (1) and a polymerized unit represented by the formula (2), based on the total of the polymerized unit represented by the formula (1) and the polymerized unit represented by the formula (2), The proportion of the polymerized unit represented by the formula 1 is preferably 40 mol% or more and less than 100 mol%, and 50 mol% or more and 1 mol%.
Less than 00 mol% is more preferred. Formula 2 with respect to the sum of the polymerized unit represented by Formula 1 and the polymerized unit represented by Formula 2
Is preferably more than 0 mol% and 60 mol% or less, more preferably more than 0 mol% and 50 mol% or less. By setting the proportion of the polymerized unit represented by the formula 1 to 40 mol% or more, the solubility of the fluoropolymer in an aqueous alkali solution is improved.
【００１９】フッ素系重合体の数平均分子量は、１×１
０3 〜３×１０4 であることが好ましく、２×１０3 〜
２×１０4 であることがより好ましい。数平均分子量が
１×１０3 未満では、造膜性が著しく悪化して均一なコ
ーティング膜を得られないことがあり、また３×１０4
超では、アルカリ水溶液に対する溶解性が充分でない場
合がある。The number average molecular weight of the fluoropolymer is 1 × 1
0 3 to 3 × 10 4 , preferably 2 × 10 3 to
More preferably, it is 2 × 10 4 . The number average molecular weight is less than 1 × 10 3, may film-forming property can not be obtained significantly worsening uniform coating film, also 3 × 10 4
If it is higher, the solubility in an aqueous alkali solution may not be sufficient.
【００２０】本発明のコーティング組成物は、通常は、
上記フッ素系重合体を溶媒中に溶解したものである。溶
媒としては、水、有機溶媒または水と有機溶媒の混合溶
媒が使用できる。本発明のコーティング組成物は、特に
フォトレジスト層などに塗布する反射防止コーティング
組成物として有用である。反射防止コーティング組成物
の溶媒としては、反射防止コーティング組成物をフォト
レジスト層に塗布する際、フォトレジスト膜にダメージ
を与えないものから選択することが好ましい。The coating composition of the present invention usually comprises
It is obtained by dissolving the above-mentioned fluoropolymer in a solvent. As the solvent, water, an organic solvent or a mixed solvent of water and an organic solvent can be used. The coating composition of the present invention is particularly useful as an antireflection coating composition applied to a photoresist layer or the like. The solvent for the antireflection coating composition is preferably selected from those that do not damage the photoresist film when the antireflection coating composition is applied to the photoresist layer.
【００２１】好ましい溶媒例として、水単独、または水
とメタノール、エタノール、イソプロパノール、２，
２，３，３，３−ペンタフルオロプロパノールなどのア
ルコール類との混合溶媒が挙げられる。混合溶媒中のア
ルコール類の割合が多いと、例えばフォトレジスト層に
ダメージを与える場合があるため、４０重量％以下が好
ましく、２０重量％以下がさらに好ましい。Preferred examples of the solvent include water alone or water and methanol, ethanol, isopropanol,
A mixed solvent with an alcohol such as 2,3,3,3-pentafluoropropanol is exemplified. If the proportion of alcohols in the mixed solvent is large, for example, the photoresist layer may be damaged, so the content is preferably 40% by weight or less, more preferably 20% by weight or less.
【００２２】コーティング組成物中のフッ素系重合体の
濃度は、フッ素系重合体が溶解する範囲内であれば特に
限定されず、所望のコーティング膜厚を得られるように
設定すればよいが、通常１〜１０重量％の範囲である。The concentration of the fluoropolymer in the coating composition is not particularly limited as long as it is within a range in which the fluoropolymer is dissolved, and may be set so as to obtain a desired coating film thickness. It is in the range of 1 to 10% by weight.
【００２３】本発明の組成物に、塗布時の濡れ性、塗膜
の均一性を改善するなどの目的で、フッ素系有機酸のア
ミン塩などの界面活性剤を添加できる。添加量は多すぎ
ると塗膜の白化を招いたり、反射防止膜下層のフォトレ
ジスト膜中に拡散して露光不良を引き起こすおそれがあ
るため、フッ素系重合体に対して１０重量％以下が好ま
しく、５重量％以下がさらに好ましい。A surfactant such as an amine salt of a fluorinated organic acid can be added to the composition of the present invention for the purpose of improving wettability at the time of coating and uniformity of the coating film. If the addition amount is too large, it may cause whitening of the coating film or diffuse into the photoresist film below the antireflection film to cause poor exposure. Therefore, the addition amount is preferably 10% by weight or less based on the fluoropolymer, More preferably, it is at most 5% by weight.
【００２４】フォトレジストを用いたフォトリソグラフ
ィによってパターンを形成するにあたり、フォトレジス
ト層表面に本発明のコーティング組成物から形成された
反射防止膜を有するフォトレジスト層を使用できる。In forming a pattern by photolithography using a photoresist, a photoresist layer having an antireflection film formed from the coating composition of the present invention on the surface of the photoresist layer can be used.
【００２５】フォトレジスト層表面に、本発明の組成物
により反射防止膜を形成する方法としては、塗膜の均一
性、簡便性の観点よりスピンコート法が好適に採用され
る。また、通常はコート後に溶剤を除去する目的でホッ
トプレートまたはオーブンにより乾燥を行うのが一般的
である。乾燥条件としては、例えばホットプレートの場
合、８０〜１００℃の温度で３０〜２００秒間の条件が
例示される。As a method for forming an antireflection film on the surface of the photoresist layer using the composition of the present invention, a spin coating method is suitably employed from the viewpoints of uniformity and simplicity of the coating film. In general, drying is carried out using a hot plate or an oven for the purpose of removing the solvent after coating. As a drying condition, for example, in the case of a hot plate, a condition at a temperature of 80 to 100 ° C. for 30 to 200 seconds is exemplified.
【００２６】反射防止膜の膜厚は、公知の反射防止理論
に従って設定すればよく、膜厚を「（露光波長）／（４
×（反射防止膜の屈折率））」の奇数倍とすることが、
反射防止性能が大きくなるため好ましい。The thickness of the anti-reflection film may be set in accordance with a known anti-reflection theory, and the thickness is set to “(exposure wavelength) / (4
× (refractive index of the antireflection film))).
This is preferable because the antireflection performance increases.
【００２７】本発明のコーティング組成物をフォトレジ
スト層の反射防止コーティング組成物として用いる場
合、適用可能なフォトレジストには特に制限はなく、ｇ
線用、ｉ線用、またはＡｒＦ、ＫｒＦなどのエキシマー
レーザ用のフォトレジストに対して効果を発揮する。特
に、反射防止膜下層のフォトレジストが露光により生成
したプロトンの触媒作用を利用する、いわゆる化学増幅
型レジストである場合、露光後の大気中での放置時間が
長くなるとレジスト表面が変質する場合があるが、本発
明の組成物により形成された塗膜はその変質を防止する
保護膜としても作用する。When the coating composition of the present invention is used as an antireflective coating composition for a photoresist layer, the applicable photoresist is not particularly limited, and g
It is effective for photoresists for lines, i-lines, or excimer lasers such as ArF and KrF. In particular, when the photoresist under the anti-reflection film is a so-called chemically amplified resist that utilizes the catalytic action of protons generated by exposure, if the exposure time in air is prolonged, the resist surface may deteriorate. However, the coating film formed by the composition of the present invention also functions as a protective film for preventing the deterioration.
【００２８】[0028]
【実施例】以下、合成例（例１〜２）、実施例（例３〜
６）を挙げて本発明をさらに具体的に説明するが、本発
明はこれらに限定されない。EXAMPLES The synthesis examples (Examples 1 and 2) and the Examples (Examples 3 to 5)
The present invention will be described more specifically with reference to 6), but the present invention is not limited to these.
【００２９】［例１］ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＯ
ＯＣＨ3 の３０６ｇを撹拌機付きの５００ｃｃオートク
レーブに仕込み、系内を窒素にて置換し内圧１ｋｇ／ｃ
ｍ2 Ｇにした。ペルフルオロブタノイルペルパーオキシ
ドの５％ＨＣＦＣ−２２５（１，３−ジクロロ−１，
１，２，２，３−ペンタフロロプロパン）溶液８６ｇを
添加し、内温を４０℃に昇温、重合反応させた。５．５
時間後、内圧が１．８ｋｇ／ｃｍ2 Ｇまで上昇し、その
後、内圧の上昇はみられなくなり、重合終了とした。[Example 1] CF 2 = CFOCF 2 CF 2 CO
306 g of OCH 3 was charged into a 500 cc autoclave equipped with a stirrer, the inside of the system was replaced with nitrogen, and the internal pressure was 1 kg / c.
m 2 G. 5% HCFC-225 of perfluorobutanoyl peroxide (1,3-dichloro-1,
86 g of (1,2,2,3-pentafluoropropane) solution was added, the internal temperature was raised to 40 ° C., and a polymerization reaction was performed. 5.5
After a lapse of time, the internal pressure increased to 1.8 kg / cm 2 G. Thereafter, the internal pressure did not increase and the polymerization was terminated.
【００３０】重合終了後、減圧にてＨＣＦＣ−２２５を
留去、さらに加熱、減圧にてＣＦ2＝ＣＦＯＣＦ2 ＣＦ2
ＣＯＯＣＨ3 を留去した。得られたＣＦ2 ＝ＣＦＯＣ
Ｆ2ＣＦ2 ＣＯＯＣＨ3 単独重合体の数平均分子量をＧ
ＰＣ法により求めたところ、約４．５×１０3 であっ
た。After completion of the polymerization, HCFC-225 was distilled off under reduced pressure, and further heated and reduced pressure to obtain CF 2 = CFOCF 2 CF 2.
COOCH 3 was distilled off. Obtained CF 2 = CFOC
The number average molecular weight of F 2 CF 2 COOCH 3 homopolymer is represented by G
It was about 4.5 × 10 3 as determined by the PC method.
【００３１】この単独重合体を加水分解することによ
り、重合単位−ＣＦ2 ＣＦ（ＯＣＦ2ＣＦ2 ＣＯＯＨ）
−からなるフッ素系重合体（以下、重合体Ａという）を
得た。さらに、２９％アンモニア水溶液にて重合体Ａの
アンモニウム塩化を行い、過剰のアンモニアおよび水を
留去して、重合単位−ＣＦ2 ＣＦ（ＯＣＦ2 ＣＦ2 ＣＯ
ＯＮＨ4 ）−からなるフッ素系重合体（以下、重合体Ｂ
という）を得た。By hydrolyzing this homopolymer, polymerized units —CF 2 CF (OCF 2 CF 2 COOH)
-A fluorine-containing polymer (hereinafter referred to as polymer A) was obtained. Further, the polymer A is ammonium chlorided with a 29% aqueous ammonia solution, excess ammonia and water are distilled off, and the polymerized unit —CF 2 CF (OCF 2 CF 2 CO
ONH 4 ) —fluorine-based polymer (hereinafter referred to as polymer B)
).
【００３２】［例２］ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＯ
ＯＣＨ3 の２２０ｇ、ペルフルオロブタノイルペルオキ
シドの５％ＨＣＦＣ−２２５溶液３ｇを撹拌機付きの２
００ｃｃオートクレーブに仕込み系内を窒素にて置換し
た。この系を液体窒素にて冷却、脱気した後、ＴＦＥ
（テトラフルオロエチレン）９ｇを導入し、内圧２．５
ｋｇ／ｃｍ2 Ｇにした。さらに内温を４０℃に昇温、重
合反応させた。Example 2 CF 2 = CFOCF 2 CF 2 CO
220 g of OCH 3 and 3 g of a 5% HCFC-225 solution of perfluorobutanoyl peroxide were added to 2 parts with a stirrer.
A 00 cc autoclave was charged and the inside of the system was replaced with nitrogen. After cooling and degassing this system with liquid nitrogen, TFE
(Tetrafluoroethylene) 9 g was introduced, and the internal pressure was 2.5
kg / cm 2 G. Further, the internal temperature was raised to 40 ° C. to cause a polymerization reaction.
【００３３】３．０時間後、内圧が１．２ｋｇ／ｃｍ2
Ｇまで下降し、その後、内圧の下降はみられなくなり、
重合終了とした。重合終了後、ＴＦＥをパージし、減圧
にてＨＣＦＣ−２２５を留去、さらに加熱、減圧にてＣ
Ｆ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＯＯＣＨ3 を留去した。After 3.0 hours, the internal pressure is 1.2 kg / cm 2
G, then the internal pressure no longer decreases,
The polymerization was completed. After completion of the polymerization, TFE was purged, HCFC-225 was distilled off under reduced pressure, and further heating and C
F 2 = CFOCF 2 CF 2 COOCH 3 was distilled off.
【００３４】得られたＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＯ
ＯＣＨ3 とＴＦＥの共重合体は、Ｆ−ＮＭＲ法によりＣ
Ｆ2 ＝ＣＦＯＣＦ2 ＣＦ2 ＣＯＯＣＨ3 ／ＴＦＥを１／
１のモル比で含むものであった。また、この共重合体の
数平均分子量をＧＰＣ法により求めたところ、約８．７
×１０3 であった。Obtained CF 2 = CFOCF 2 CF 2 CO
The copolymer of OCH 3 and TFE is converted to C by F-NMR.
F 2 = CFOCF 2 CF 2 COOCH 3 / TFE
It was contained in a molar ratio of 1. When the number average molecular weight of this copolymer was determined by GPC, it was found to be about 8.7.
× 10 3 .
【００３５】この共重合体を加水分解することにより、
重合単位−（ＣＦ2 ＣＦ2 ）−と重合単位−ＣＦ2 ＣＦ
（ＯＣＦ2 ＣＦ2 ＣＯＯＨ）−からなるフッ素系重合体
（以下、重合体Ｃという）を得た。さらに、２９％アン
モニア水溶液にて重合体Ｃのアンモニウム塩化を行い、
過剰のアンモニアおよび水を留去して、重合単位−（Ｃ
Ｆ2 ＣＦ2 ）−と重合単位−ＣＦ2 ＣＦ（ＯＣＦ2 ＣＦ
2 ＣＯＯＮＨ4 ）−がモル比１／１からなるフッ素系重
合体（以下、重合体Ｄという）を得た。By hydrolyzing this copolymer,
Polymerized unit — (CF 2 CF 2 ) — and polymerized unit —CF 2 CF
A fluorine-based polymer (hereinafter, referred to as polymer C) composed of (OCF 2 CF 2 COOH) — was obtained. Further, ammonium chloride of polymer C is performed with a 29% aqueous ammonia solution,
Excess ammonia and water are distilled off to give polymerized units-(C
F 2 CF 2 ) — and polymerized units —CF 2 CF (OCF 2 CF)
2 COONH 4 )-was obtained as a fluoropolymer having a molar ratio of 1/1 (hereinafter referred to as polymer D).
【００３６】［例３］重合体Ａを水／メタノール混合溶
媒（メタノール含有量２０重量％）に溶解させ、重合体
濃度５重量％の反射防止コーティング用組成物を調製
し、次の評価１および評価２を行った。その結果、屈折
率は１．３６、膜厚は６７ｎｍであった。また、フォト
レジストのパターン上には、残渣、異物などは観察され
ず、反射防止膜はレジスト現像時に完全に除去できるこ
とを確認した。Example 3 Polymer A was dissolved in a water / methanol mixed solvent (methanol content: 20% by weight) to prepare a composition for an antireflection coating having a polymer concentration of 5% by weight. Evaluation 2 was performed. As a result, the refractive index was 1.36 and the film thickness was 67 nm. Further, no residue, foreign matter, etc. were observed on the photoresist pattern, and it was confirmed that the antireflection film could be completely removed during resist development.
【００３７】（評価１：塗膜の屈折率および膜厚の測
定）反射防止コーティング用組成物をスピンコート法に
よりシリコンウェハ上に塗布し、塗膜の屈折率および膜
厚をエリプソメータにより測定した。(Evaluation 1: Measurement of Refractive Index and Film Thickness of Coating Film) The antireflection coating composition was applied on a silicon wafer by a spin coating method, and the refractive index and the film thickness of the coating film were measured by an ellipsometer.
【００３８】（評価２：フォトレジスト現像時の反射防
止膜除去特性の評価）ヘキサメチルシラザン雰囲気中に
５分間放置することにより表面処理したシリコンウェハ
上に、フォトレジストＴＨＭＲ−ｉＰ１７００（東京応
化工業社製）をスピンコート法により塗布、ホットプレ
ート上で９０℃、９０秒間乾燥させることにより膜厚１
μｍのレジスト層を形成した。(Evaluation 2: Evaluation of anti-reflection film removal characteristics at the time of photoresist development) A photoresist THMR-iP1700 (Tokyo Ohka Kogyo Co., Ltd.) Co., Ltd.) by spin coating and drying on a hot plate at 90 ° C. for 90 seconds to obtain a film thickness of 1
A μm resist layer was formed.
【００３９】次いで反射防止コーティング用組成物をス
ピンコートし、ホットプレート上で９０℃、６０秒間乾
燥することにより、反射防止層を形成した。このときの
スピンコート条件は、評価１と同一条件とした。次にテ
ストパターンを介してｉ線（３６５ｎｍ）により露光を
行い、その後露光後ベーク（ＰＥＤ）を行った。次いで
現像液（２．３８重量％テトラメチルアンモニウムヒド
ロキシド水溶液）を用いて６５秒間パドル現像を行った
後に、超純水にてリンスし、フォトレジストのパターン
を得た。Next, the composition for antireflection coating was spin-coated and dried on a hot plate at 90 ° C. for 60 seconds to form an antireflection layer. The spin coating conditions at this time were the same as those in Evaluation 1. Next, exposure was performed by i-line (365 nm) through a test pattern, and then post-exposure bake (PED) was performed. Subsequently, paddle development was performed for 65 seconds using a developing solution (2.38% by weight aqueous solution of tetramethylammonium hydroxide), followed by rinsing with ultrapure water to obtain a photoresist pattern.
【００４０】このサンプルについて金属顕微鏡観察を行
い、現像時に反射防止膜が充分に除去できているかを評
価した。The sample was observed with a metallographic microscope to evaluate whether the antireflection film was sufficiently removed during development.
【００４１】［例４］重合体Ａを重合体Ｂに変更した以
外は、例３と同様にして評価１および評価２を行った。
結果を以下に示す。 （評価１）屈折率１．３７、膜厚６６ｎｍ。 （評価２）フォトレジストのパターン上には、残渣、異
物などは観察されず、反射防止膜はレジスト現像時に完
全に除去できることを確認した。Example 4 Evaluations 1 and 2 were carried out in the same manner as in Example 3 except that the polymer A was changed to the polymer B.
The results are shown below. (Evaluation 1) Refractive index 1.37, film thickness 66 nm. (Evaluation 2) No residue, foreign matter, etc. were observed on the photoresist pattern, and it was confirmed that the antireflection film could be completely removed during the resist development.
【００４２】［例５］重合体Ａを重合体Ｃに変更した以
外は、例３と同様にして評価１および評価２を行った。
結果を以下に示す。 （評価１）屈折率１．３５、膜厚６８ｎｍ。 （評価２）フォトレジストのパターン上には、残渣、異
物などは観察されず、反射防止膜はレジスト現像時に完
全に除去できることを確認した。Example 5 Evaluations 1 and 2 were conducted in the same manner as in Example 3 except that the polymer A was changed to the polymer C.
The results are shown below. (Evaluation 1) Refractive index 1.35, film thickness 68 nm. (Evaluation 2) No residue, foreign matter, etc. were observed on the photoresist pattern, and it was confirmed that the antireflection film could be completely removed during the resist development.
【００４３】［例６］重合体Ａを重合体Ｄに変更し、溶
媒を水単独とした以外は、例３と同様にして評価１およ
び評価２を行った。結果を以下に示す。 （評価１）屈折率１．３７、膜厚６６ｎｍ。 （評価２）フォトレジストのパターン上には、残渣、異
物などは観察されず、反射防止膜はレジスト現像時に完
全に除去できることを確認した。Example 6 Evaluations 1 and 2 were conducted in the same manner as in Example 3 except that the polymer A was changed to the polymer D and the solvent was water alone. The results are shown below. (Evaluation 1) Refractive index 1.37, film thickness 66 nm. (Evaluation 2) No residue, foreign matter, etc. were observed on the photoresist pattern, and it was confirmed that the antireflection film could be completely removed during the resist development.
【００４４】[0044]
【発明の効果】本発明は、特にフォトレジスト層表面の
反射防止膜として適切な低屈折率を有し、かつフォトレ
ジスト現像時に、現像液によって完全に除去できる反射
防止膜を形成できるコーティング組成物として有用であ
る。この組成物を用いることにより、パターン形成プロ
セスの高歩留まり化に寄与する。According to the present invention, there is provided a coating composition having a low refractive index suitable as an antireflection film particularly on the surface of a photoresist layer and capable of forming an antireflection film which can be completely removed by a developing solution at the time of developing the photoresist. Useful as Use of this composition contributes to a high yield of the pattern formation process.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 柏木 王明 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Ouaki Kashiwagi 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd.
Claims (3)
系重合体または下記式１で表される重合単位と下記式２
で表される重合単位とを含むフッ素系重合体を含有する
ことを特徴とするコーティング組成物。 【化１】−ＣＦ2 ＣＦ（ＯＲｆＣＯＯＭ）− 式１ −ＣＦ2 ＣＦＸ− 式２ ［式中、Ｒｆはエーテル性酸素原子を含んでもよい直鎖
状または分岐状のペルフルオロアルキレン基、−ＣＯＯ
Ｍは−ＣＯＯＨ、−ＣＯＯＹ（Ｙは置換されていてもよ
いアンモニウムイオン）、または−ＣＯＯＨ・Ｚ（Ｚは
アミン）、Ｘはフッ素原子または塩素原子である。］1. A fluorine-containing polymer containing a polymer unit represented by the following formula (1) or a polymer unit represented by the following formula (1):
A coating composition comprising a fluorine-based polymer containing a polymerized unit represented by the formula: ## STR1 ## -CF 2 CF (ORfCOOM) - Formula 1 -CF 2 CFX- Formula 2 [wherein, Rf is etheric oxygen atom which may contain linear or branched perfluoroalkylene group, -COO
M is -COOH, -COOY (Y is an ammonium ion which may be substituted), or -COOH.Z (Z is an amine), and X is a fluorine atom or a chlorine atom. ]
3 〜３×１０4 である請求項１記載のコーティング組成
物。2. The number average molecular weight of the fluoropolymer is 1 × 10
3. The coating composition according to claim 1, wherein the coating composition is 3 to 3 × 10 4 .
ィによってパターンを形成するにあたり、フォトレジス
ト層表面に請求項１または２記載のコーティング組成物
から形成された反射防止膜を有するフォトレジスト層を
使用することを特徴とするパターン形成方法。3. A method of forming a pattern by photolithography using a photoresist, comprising using a photoresist layer having an antireflection film formed from the coating composition according to claim 1 on the surface of the photoresist layer. A pattern forming method characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29205197A JP3965740B2 (en) | 1997-10-24 | 1997-10-24 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29205197A JP3965740B2 (en) | 1997-10-24 | 1997-10-24 | Coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11124531A true JPH11124531A (en) | 1999-05-11 |
| JP3965740B2 JP3965740B2 (en) | 2007-08-29 |
Family
ID=17776910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29205197A Expired - Fee Related JP3965740B2 (en) | 1997-10-24 | 1997-10-24 | Coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3965740B2 (en) |
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| WO2006011607A1 (en) * | 2004-07-30 | 2006-02-02 | Tokyo Ohka Kogyo Co., Ltd. | Material for forming resist protective film and method for forming resist pattern using same |
| JP2006100514A (en) * | 2004-09-29 | 2006-04-13 | Dainippon Screen Mfg Co Ltd | Removing device, protective film forming device, substrate processing system and removing method |
| JP2006308647A (en) * | 2005-04-26 | 2006-11-09 | Shin Etsu Chem Co Ltd | Resist protective film material and pattern forming method |
| WO2007042348A1 (en) * | 2005-10-13 | 2007-04-19 | International Business Machines Corporation | Top antireflective coating composition with low refractive index at 193nm radiation wavelength |
| KR101054729B1 (en) | 2005-10-13 | 2011-08-05 | 인터내셔널 비지네스 머신즈 코포레이션 | Top antireflective coating composition with low refractive index at radiation wavelength of 193 nm |
| US7544750B2 (en) | 2005-10-13 | 2009-06-09 | International Business Machines Corporation | Top antireflective coating composition with low refractive index at 193nm radiation wavelength |
| US7964659B2 (en) * | 2007-02-22 | 2011-06-21 | Asahi Glass Company, Limited | Antireflection coating composition |
| WO2008102820A1 (en) | 2007-02-22 | 2008-08-28 | Asahi Glass Company, Limited | Composition for antireflective coating |
| WO2015080061A1 (en) * | 2013-11-29 | 2015-06-04 | 旭硝子株式会社 | Coating composition, and method for producing photoresist laminate |
| JP2017197718A (en) * | 2016-04-22 | 2017-11-02 | 旭硝子株式会社 | Coating composition and method for producing photoresist laminate |
| US10416561B2 (en) | 2016-04-22 | 2019-09-17 | AGC Inc. | Coating composition, and process for producing photoresist laminate |
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