JP2005091407A - Method for evaluating radiation-sensitive resin and radiation-sensitive resin composition - Google Patents
Method for evaluating radiation-sensitive resin and radiation-sensitive resin composition Download PDFInfo
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- JP2005091407A JP2005091407A JP2003320589A JP2003320589A JP2005091407A JP 2005091407 A JP2005091407 A JP 2005091407A JP 2003320589 A JP2003320589 A JP 2003320589A JP 2003320589 A JP2003320589 A JP 2003320589A JP 2005091407 A JP2005091407 A JP 2005091407A
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- radiation
- resin
- sensitive resin
- solution
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- 229920005989 resin Polymers 0.000 title claims abstract description 140
- 230000005855 radiation Effects 0.000 title claims abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 28
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- 238000009792 diffusion process Methods 0.000 claims abstract description 39
- 238000011161 development Methods 0.000 claims abstract description 23
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- 238000005259 measurement Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
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- CEZIJESLKIMKNL-UHFFFAOYSA-N 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium Chemical compound C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 CEZIJESLKIMKNL-UHFFFAOYSA-N 0.000 description 4
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Abstract
Description
本発明は、感放射線性樹脂の評価方法およびこの評価方法を用いた感放射線性樹脂組成物、特にKrFエキシマレーザーあるいはArFエキシマレーザー等の遠紫外線、シンクロトロン放射線等のX線、電子線等の荷電粒子線の如き各種の放射線を使用する微細加工に有用な化学増幅型レジストとして好適に使用できる感放射線性樹脂組成物に関する。 The present invention relates to a method for evaluating a radiation sensitive resin and a radiation sensitive resin composition using this evaluation method, in particular, far ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, electron beams, etc. The present invention relates to a radiation sensitive resin composition that can be suitably used as a chemically amplified resist useful for microfabrication using various types of radiation such as charged particle beams.
集積回路素子の製造に代表される微細加工の分野においては、より高い集積度を得るために、最近ではArFエキシマレーザー(波長193nm)、F2エキシマレーザー(波長157nm)等を用いた100nm以下のレベルでの微細加工が可能なリソグラフィー技術が必要とされている。このようなエキシマレーザーによる照射に適した感放射線性樹脂組成物として、酸解離性官能基を有する成分と放射線の照射により酸を発生する成分である酸発生剤とによる化学増幅効果を利用した化学増幅型感放射線性樹脂組成物が数多く提案されている。
例えば、感放射線性樹脂組成物として、2−アルキル−2−アダマンチル基、または1−アダマンチル−1−アルキルアダマンチル基で保護されたアルカリ可溶性を有し、それ自身ではアルカリに不溶または難溶であるが、酸の作用でアルカリに可溶となる樹脂と特定のスルホニウム塩系酸発生剤を含有する化学増幅型ポジ型レジスト組成物(特許文献1参照)。特定の基板密着性脂環式エステルと特定の脂環式骨格を有する酸脱離性のエステルに、第3成分として上記2成分の中間の極性を持つ特定の脂環式エステルを加えて3元共重合させたフォトレジスト用高分子化合物(特許文献2参照)、同じく脂環式骨格を有する特定構造の3種の単量体ユニットを特定の割合で含む樹脂(特許文献3参照)等が知られている。
また、これらの感放射線性樹脂組成物に用いられる樹脂は、感放射線性樹脂組成物としたときの解像度や透過率により、あるいは樹脂と溶媒との溶解度パラメーターにより、それぞれ評価されてきた。
In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, an ArF excimer laser (wavelength 193 nm), an F 2 excimer laser (wavelength 157 nm) or the like is used. There is a need for a lithography technique that enables fine processing at a level. As a radiation-sensitive resin composition suitable for irradiation with such an excimer laser, a chemical utilizing the chemical amplification effect by the component having an acid-dissociable functional group and the acid generator which is a component generating an acid by irradiation with radiation. Many amplification type radiation sensitive resin compositions have been proposed.
For example, the radiation-sensitive resin composition has alkali solubility protected with a 2-alkyl-2-adamantyl group or 1-adamantyl-1-alkyladamantyl group, and is itself insoluble or hardly soluble in alkali. However, a chemically amplified positive resist composition containing a resin that is soluble in alkali by the action of an acid and a specific sulfonium salt-based acid generator (see Patent Document 1). Three-component by adding a specific alicyclic ester having an intermediate polarity between the above two components as a third component to an acid-eliminating ester having a specific substrate adhesion alicyclic ester and a specific alicyclic skeleton. Known are polymer compounds for photoresist (see Patent Document 2), resins containing three types of monomer units having a specific structure having an alicyclic skeleton in a specific ratio (see Patent Document 3), and the like. It has been.
Moreover, the resin used for these radiation sensitive resin compositions has been evaluated by the resolution and transmittance when the radiation sensitive resin composition is used, or by the solubility parameter of the resin and the solvent, respectively.
しかしながら、半導体分野において、より高い集積度が求められるようになると、レジストである感放射線性樹脂組成物はより優れた解像度が必要とされるようになってきた。次世代の半導体素子等は現世代以上に微細なパターンを必要とするため、今まで以上にウエハー内でのパターン寸法の均一性、および、パターン解像欠損の発生し易さの改善が求められるようになってきた。これらの課題を克服するためには、感放射線性樹脂組成物としての解像性能等の向上もさることながら、樹脂としての解像性や溶解性能の均一性を従来以上に厳格に判断する必要が出てきたが、従来の解像性や溶解性能の均一性に対する評価方法では十分でないという問題がある。
解決しようとする課題は、感放射線性樹脂の微小な解像性や溶解性の僅かな相違点を評価する評価方法がないことである。
また、評価方法がないため、従来のレジスト性能を維持したまま、現像欠陥を発生することがなく、またLER特性に優れた感放射線性樹脂組成物が得られないことである。
The problem to be solved is that there is no evaluation method for evaluating slight differences in minute resolution and solubility of the radiation-sensitive resin.
Further, since there is no evaluation method, development defects are not generated while maintaining conventional resist performance, and a radiation-sensitive resin composition having excellent LER characteristics cannot be obtained.
本発明の評価方法は、感放射線性樹脂のレジスト溶剤溶液の動的光散乱を測定し、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数(kD)により感放射線性樹脂の現像特性を評価することを特徴とする。ここで、現像特性とは現像欠陥およびラインエッジラフネス(LER)をいう。
上記係数(kD)は溶液の濃度変化に伴う拡散係数変化を表す。また、溶液の濃度変化時の濃度とはレジストがウエハー上にスピン塗布されるときの濃度変化を想定することができるので、係数(kD)は塗布後の膜中に生成する樹脂成分の拡散係数から求められる流体力学半径の平均値を間接的に表す指標となる。
この係数(kD)は、その値が正の値であった場合、高濃度でも樹脂同士の接触・絡まりが見られず結果として塗布後に樹脂成分の凝集を形成し難いが、負の値であった場合、高濃度で樹脂同士の接触・絡まりが見られ、この係数(kD)の微小な変化で生成する樹脂成分の凝集体(クラスター)分布の大小に大きく影響することが分かった。このため、係数(kD)は非常に重要な値であると考えられる。特に、未露光部の現像液に対する溶解性が乏しいArF用途のポリアクリル酸エステルベースの樹脂を用いる場合、その樹脂成分の凝集体の流体力学半径の分布ばらつきが現像液に対する溶解性のばらつきに反映され、現像欠陥やLERのロット間差へと結びつく可能性があることが見出された。このため、係数(kD)を測定することにより、レジストをその原料段階で評価・選別できることが分かった。本発明はこのような知見に基づくものである。
The evaluation method of the present invention measures dynamic light scattering of a resist solvent solution of a radiation sensitive resin, and uses a coefficient (k D ) representing a change in diffusion coefficient of the radiation sensitive resin in the solution accompanying a change in concentration of the solution. It is characterized by evaluating the development characteristics of a radiation sensitive resin. Here, the development characteristics refer to development defects and line edge roughness (LER).
The coefficient (k D ) represents a change in diffusion coefficient accompanying a change in solution concentration. Further, since the concentration at the time of changing the concentration of the solution can be assumed to be a concentration change when the resist is spin-coated on the wafer, the coefficient (k D ) is a diffusion of the resin component generated in the coated film. This is an index that indirectly represents the average value of the hydrodynamic radius obtained from the coefficient.
If this coefficient (k D ) is a positive value, contact and entanglement between the resins are not seen even at high concentrations, and as a result, it is difficult to form agglomeration of resin components after coating, but a negative value In such a case, the contact / entanglement between the resins was observed at a high concentration, and it was found that the size of the aggregate (cluster) distribution of the resin component produced by a minute change in this coefficient (k D ) was greatly affected. For this reason, the coefficient (k D ) is considered to be a very important value. In particular, when using a polyacrylate ester-based resin for ArF, which has poor solubility in the developer in the unexposed area, the dispersion in the hydrodynamic radius of the aggregate of the resin component is reflected in the dispersion in the solubility in the developer. It has been found that this may lead to development defects and LER lot-to-lot differences. For this reason, it was found that the resist can be evaluated and selected at the raw material stage by measuring the coefficient (k D ). The present invention is based on such knowledge.
本発明の感放射線性樹脂組成物は、アルカリ不溶性またはアルカリ難溶性であって酸の作用によりアルカリ易溶性となる酸解離性基含有樹脂(A)を単独または2種以上と、レジスト溶剤(B)と、感放射線性酸発生剤(C)とを含有し、上記酸解離性基含有樹脂(A)の少なくとも1種は、該樹脂(A)のレジスト溶剤(B)溶液の動的光散乱測定により、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数(kD)が−2.20g/g以上であることを特徴とする。すなわち、酸解離性基含有樹脂(A)を複数含有する場合には、それらのうち少なくとも1つの樹脂(A)のkD値が−2.20g/g以上であることを特徴とする。 The radiation-sensitive resin composition of the present invention comprises an acid-dissociable group-containing resin (A) which is alkali-insoluble or hardly soluble in alkali and easily soluble in alkali by the action of an acid, or a resist solvent (B ) And a radiation sensitive acid generator (C), and at least one of the acid dissociable group-containing resins (A) is a dynamic light scattering of a resist solvent (B) solution of the resin (A). According to the measurement, a coefficient (k D ) representing a change in diffusion coefficient of the radiation-sensitive resin in the solution accompanying a change in the concentration of the solution is −2.20 g / g or more. That is, when a plurality of acid dissociable group-containing resins (A) are contained, at least one of the resins (A) has a k D value of −2.20 g / g or more.
本発明の評価方法は、樹脂溶液の動的光散乱を測定し、その濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数(kD)により感放射線性樹脂の現像欠陥を評価するので、第一に、現像欠陥の発生を抑えることができ、第二に、樹脂が形成するクラスターのサイズ分布に起因するLERを改善できる感放射線性樹脂の評価・選別が容易になる。
また、酸解離性基含有樹脂(A)と、レジスト溶剤(B)と、感放射線性酸発生剤(C)とを含有し、上記酸解離性基含有樹脂(A)は、該樹脂(A)のレジスト溶剤(B)溶液の動的光散乱測定により、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数(kD)が−2.20g/g以上であり、酸解離性基含有樹脂(A)を複数含有する場合には、それらのうち少なくとも1つの樹脂(A)のkD値が−2.20g/g以上であるので、活性放射線、特に、ArFエキシマレーザー(波長193nm)に代表される遠紫外線に感応する化学増幅型レジストとして、放射線に対する透明性が高く、感度、解像度、ドライエッチング耐性、パターン形状も良好であるレジストとしての基本的性能を有しているだけでなく、第一に、現像欠陥の発生を抑えることができ、第二に、樹脂の粒経分布に起因するLERを改善することができ、今後さらに微細化が進むと予想される半導体デバイスの製造に極めて好適に使用することができる。
The evaluation method of the present invention measures the dynamic light scattering of a resin solution, and develops development defects of the radiation-sensitive resin by a coefficient (k D ) representing a change in diffusion coefficient in the solution of the radiation-sensitive resin accompanying the concentration change. Since evaluation is performed, firstly, the occurrence of development defects can be suppressed, and secondly, evaluation and selection of a radiation-sensitive resin that can improve LER caused by the size distribution of clusters formed by the resin is facilitated.
Further, it contains an acid-dissociable group-containing resin (A), a resist solvent (B), and a radiation-sensitive acid generator (C), and the acid-dissociable group-containing resin (A) is a resin (A). ) Of the resist solvent (B) solution, the coefficient (k D ) representing the diffusion coefficient change in the solution of the radiation sensitive resin accompanying the change in the concentration of the solution is −2.20 g / g or more. Yes, when a plurality of acid-dissociable group-containing resins (A) are contained, the k D value of at least one of the resins (A) is −2.20 g / g or more, so actinic radiation, in particular, As a chemically amplified resist sensitive to far-ultraviolet rays typified by an ArF excimer laser (wavelength 193 nm), it has basic performance as a resist with high transparency to radiation, sensitivity, resolution, dry etching resistance, and good pattern shape. I just have it First, it is possible to suppress development defects, and second, it is possible to improve the LER caused by the particle size distribution of the resin, and for the production of semiconductor devices that are expected to be further miniaturized in the future. It can be used very suitably.
樹脂溶液の動的光散乱を測定するための動的光散乱測定装置は、ドイツALV社製光散乱装置を用いた。この装置の仕様は、ゴニオメータとしてALV/DLS/SLS−5022F(Attenuator付き)、レーザー光源として波長632.8nm、22mW He−Neレーザー、散乱光検出部としてデュアル式アバランシェフォトダイオ−ド(ALV−High QE APD×2)+ビームスプリッター、相関計としてALV−5000/EPP+Fastモード測定用ALV−6010/160である。また、制御・解析プログラムはALV−5000E/WIN(ver.3)を使用した。
なお、レーザー光源としては、Arレーザー(波長488nm)、固体半導体レーザー(YAG2倍波、532nm)等を、散乱光検出部には、例えば光電子倍増管(フォトマルチプライヤー)、フォトダイオ−ド等を使用できる。
As a dynamic light scattering measuring apparatus for measuring the dynamic light scattering of the resin solution, a light scattering apparatus manufactured by ALV Germany was used. The specifications of this apparatus are as follows: ALV / DLS / SLS-5022F (with Attenuator) as a goniometer, wavelength 632.8 nm, 22 mW He-Ne laser as a laser light source, and dual avalanche photodiode (ALV-High) as a scattered light detector. QE APD × 2) + beam splitter, ALV-5000 / EPP + Fast mode measurement ALV-6010 / 160 as a correlator. The control / analysis program used was ALV-5000E / WIN (ver. 3).
As a laser light source, an Ar laser (wavelength 488 nm), a solid-state semiconductor laser (YAG double wave, 532 nm), etc. are used, and for example, a photomultiplier tube (photomultiplier), a photodiode, etc. are used as the scattered light detector. Can be used.
動的光散乱の測定原理について以下に説明する。
溶液中に溶解している物質はブラウン運動による濃度揺らぎを生じる。動的光散乱法では、溶液に干渉性の高いレーザー光などを当てて、濃度揺らぎに起因する散乱光強度の時間変化を制御コンピューターメモリー上に記憶させ、散乱光強度の時間相関関数を計算した指数型減衰曲線から、各濃度おける拡散係数を測定することができる。
一方、線状高分子一本鎖の挙動を調べるためには、希薄とされる有限濃度域の測定値の濃度ゼロ外挿から得られる無限希釈状態での拡散係数D0を用いる必要がある。
また、下の(イ)式で定義されるアインシュタイン−ストークスの関係より得られる無限希釈状態における流体力学半径RHは線状高分子一本鎖あたりの広がりを表すパラメーターとして使用される。
(イ):D0=kBT/6πηRH
ここで、D0は無限希釈状態での拡散係数、kBはボルツマン定数、Tは絶対温度、ηは溶媒粘度、RHは無限希釈状態での流体力学半径をそれぞれ表す。
The measurement principle of dynamic light scattering will be described below.
Substances dissolved in the solution cause concentration fluctuations due to Brownian motion. In the dynamic light scattering method, a laser beam with high coherence is applied to the solution, and the temporal change of the scattered light intensity caused by concentration fluctuation is stored in the control computer memory, and the time correlation function of the scattered light intensity is calculated. From the exponential decay curve, the diffusion coefficient at each concentration can be measured.
On the other hand, in order to examine the behavior of the linear polymer single chain, it is necessary to use the diffusion coefficient D 0 in the infinite dilution state obtained from the concentration zero extrapolation of the measured value in the finite concentration region that is diluted.
In addition, the hydrodynamic radius R H in the infinite dilution state obtained from the Einstein-Stokes relationship defined by the following equation (A) is used as a parameter representing the spread per linear polymer chain.
(A): D 0 = k B T / 6πηR H
Here, D 0 is the diffusion coefficient in the infinite dilution state, k B is the Boltzmann constant, T is the absolute temperature, η is the solvent viscosity, and R H is the hydrodynamic radius in the infinite dilution state.
有限濃度での拡散係数Dは、溶媒中に存在する高分子間の引力、斥力の相互作用を含んでいるため、上記D0とは異なる値をとる場合が多く、正式には「見かけ上の拡散係数」と呼ばれる。同様に、有限濃度における流体力学半径Rも正式には「見かけ上の流体力学半径」とされる。また、高分子に分子量分布がある場合には、解析法としてCONTIN法(逆ラプラス変換法)を用いることにより、z平均のDの分布を求めることができる。
なお、感放射線性樹脂組成物中の樹脂成分の分子量程度では、一般的に測定されるすべての散乱角度、例えば12〜155度の散乱角度、において質点として観測される。このため、内部運動・回転運動などに起因する拡散係数の散乱角度、すなわちq=4nπ/λ×sin(θ/2)[nは溶媒の屈折率、λはレーザービームの波長、θは散乱角度]で定義される散乱ベクトルq依存性は認められず、樹脂成分の並進拡散運動が測定される。従って、各散乱角度における拡散係数の平均値を、その濃度における「見かけ上の拡散係数」の実測値とできる。
Since the diffusion coefficient D at a finite concentration includes the interaction of attractive force and repulsive force between polymers present in the solvent, it often takes a value different from the above D 0 . It is called "diffusion coefficient". Similarly, the hydrodynamic radius R at a finite concentration is formally designated as an “apparent hydrodynamic radius”. When the polymer has a molecular weight distribution, the z-average D distribution can be obtained by using the CONTIN method (inverse Laplace transform method) as an analysis method.
In addition, the molecular weight of the resin component in the radiation-sensitive resin composition is observed as a mass point at all generally measured scattering angles, for example, a scattering angle of 12 to 155 degrees. Therefore, the scattering angle of the diffusion coefficient due to internal motion / rotational motion, ie, q = 4nπ / λ × sin (θ / 2) [n is the refractive index of the solvent, λ is the wavelength of the laser beam, and θ is the scattering angle. ], The translational diffusion motion of the resin component is measured. Therefore, the average value of the diffusion coefficient at each scattering angle can be an actual measurement value of the “apparent diffusion coefficient” at the concentration.
拡散係数D0は上述したように、動的光散乱法を用いて測定される有限濃度域の見かけ上の拡散係数D値を濃度ゼロに外挿することで得られる。拡散係数D値と濃度cとの関係を図1に示す。図1は見かけ上の拡散係数Dを縦軸に、濃度c(重量%)を横軸にして、希薄な順に、濃度c1、c2、c3に対する見かけ上の拡散係数D1、D2、D3、をプロットした図である。測定すべき濃度c(重量%)の範囲は、Dとcとの間に直線関係が成立する範囲が好ましい。Dとcとの間に成立する直線をc→0に外挿することで一義的にそのプロット図の切片の値が拡散係数D0になる。本発明において、測定すべき濃度c(重量%)の範囲は、約10重量%以下の濃度域が好ましい。約10重量%以下の濃度で直線関係が成立する。なお、樹脂成分と溶媒成分との組み合わせによっては明確な直線とならない場合があるが、その場合には直線性が良好な低濃度側でのデータを用いて直線とすることができる。
理論的な扱いでは通常濃度cの単位はg/mlを用いるのが一般的ではあるが、本発明では感放射線性樹脂組成物の調製が重量測定で行なわれているので重量%を使用した。従って、後述するkDの単位はg/gとなる。
As described above, the diffusion coefficient D 0 can be obtained by extrapolating the apparent diffusion coefficient D value in the finite concentration range measured using the dynamic light scattering method to zero concentration. The relationship between the diffusion coefficient D value and the concentration c is shown in FIG. FIG. 1 shows the apparent diffusion coefficients D 1 and D 2 for the concentrations c 1 , c 2 , and c 3 in the order of dilution, with the apparent diffusion coefficient D on the vertical axis and the concentration c (wt%) on the horizontal axis. , D 3 are plotted. The range of concentration c (% by weight) to be measured is preferably a range in which a linear relationship is established between D and c. By extrapolating a straight line formed between D and c to c → 0, the value of the intercept in the plot is uniquely the diffusion coefficient D 0 . In the present invention, the range of concentration c (wt%) to be measured is preferably a concentration range of about 10 wt% or less. A linear relationship is established at a concentration of about 10% by weight or less. In addition, although it may not become a clear straight line depending on the combination of a resin component and a solvent component, in that case, it can be made a straight line using data on the low concentration side with good linearity.
Theoretically, the unit of the concentration c is generally g / ml, but in the present invention, the radiation sensitive resin composition is prepared by weight measurement, so the weight% is used. Therefore, the unit of k D described later is g / g.
上記直線関係式は、下記(ロ)式で表される。
(ロ):D=D0(1+kDc)
本発明においては、(ロ)式における拡散係数の濃度勾配kDを用いて感放射線性樹脂の現像欠陥を評価する。
動的光散乱法を用いて測定される濃度勾配kDは、静的光散乱法により測定される第2ビリアル係数A2と密接な関係にあるとされている。第2ビリアル係数A2は高分子鎖と溶媒の相互作用を表すパラメーターとして高分子溶液物性において一般的に用いられている。具体的にはA2=0を非摂動状態であるθ状態として、溶媒和によりポリマーの広がりが理論よりも大きくなり排除体積効果が現れるA2>0を良溶媒系、逆にポリマーセグメント間に引力が働き広がりが小さくなるとされているA2<0を貧溶媒系として定義している。A2の符号が負で値が小さいほどポリマーと溶媒の相性は悪くなり、場合によっては析出、沈殿してしまう。
The linear relational expression is represented by the following (b) expression.
(B): D = D 0 (1 + k D c)
In the present invention, the development defect of the radiation sensitive resin is evaluated using the concentration gradient k D of the diffusion coefficient in the equation (b).
The concentration gradient k D measured using the dynamic light scattering method is said to be closely related to the second virial coefficient A 2 measured by the static light scattering method. The second virial coefficient A 2 is generally used in polymer solution properties as a parameter representing the interaction between the polymer chain and the solvent. Specifically, assuming that A 2 = 0 is a non-perturbed θ state, the solvation causes the polymer spread to be larger than the theoretical value, and an excluded volume effect appears. A 2 > 0 is a good solvent system, and conversely between polymer segments A 2 <0, which is considered to be that the attractive force acts and the spread becomes small, is defined as a poor solvent system. The smaller the sign of A 2 and the smaller the value, the worse the compatibility between the polymer and the solvent, and in some cases, precipitation and precipitation occur.
濃度勾配kD値は、対象物質の分子量にも依存するが、一般的にはA2>0である良溶媒系と言われている樹脂成分/溶媒の組み合わせにおいて正の値をとる。樹脂成分の溶解状態が良好であるものほどkDの値は大きくなる傾向にある。一方、kD値の値が負の値をとる場合には、濃度上昇とともに拡散係数は小さくなる。kD値が小さいほど(負の勾配が急であるほど)溶媒が貧である、即ち、ポリマーのセグメント間には引力が働き、分子内では収縮方向(粒経が小さくなる方向)に、分子間では引力が働くことにより凝集しやすい傾向にある。
以上のことから、濃度勾配kDは樹脂溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数(kD)といえる。また、このkD値が感放射線性樹脂の微小な溶解性の僅かな相違点を表しているので、この値により感放射線性樹脂の現像欠陥およびLERを評価できる。
The concentration gradient k D value depends on the molecular weight of the target substance, but generally takes a positive value in a resin component / solvent combination that is said to be a good solvent system with A 2 > 0. The better the dissolved state of the resin component, the larger the value of k D tends to be. On the other hand, when the k D value takes a negative value, the diffusion coefficient decreases as the concentration increases. The smaller the k D value (the steeper negative slope), the poorer the solvent, that is, the attractive force acts between the polymer segments, and the molecules in the shrinking direction (the direction in which the particle size decreases) In between, there is a tendency to aggregate due to the attraction.
From the above, it can be said that the concentration gradient k D is a coefficient (k D ) representing a change in diffusion coefficient in the solution of the radiation-sensitive resin accompanying a change in the concentration of the resin solution. Further, since this k D value represents a slight difference in the minute solubility of the radiation sensitive resin, the development defect and LER of the radiation sensitive resin can be evaluated by this value.
本発明方法は、ネガ型感放射線性樹脂、ポジ型感放射線性樹脂のいずれの感放射線性樹脂であっても、その現像特性を評価できる。
特に樹脂と溶媒との組み合わせにおいて、kD値が負の値をとる樹脂と溶媒との組み合わせに適用することが好ましい。
また、kD値は評価の対象となる感放射線性樹脂および溶媒の組み合わせによって異なるが、ポリアクリル酸エステルベースの樹脂とそのレジスト溶媒の場合、−2.20g/g以上、好ましくは−2.10g/g以上である。
The method of the present invention can evaluate the development characteristics of any radiation sensitive resin of negative type radiation sensitive resin and positive type radiation sensitive resin.
In particular, the combination of a resin and a solvent is preferably applied to a combination of a resin and a solvent having a negative k D value.
The k D value varies depending on the combination of the radiation-sensitive resin and the solvent to be evaluated, but in the case of a polyacrylate ester-based resin and its resist solvent, it is −2.20 g / g or more, preferably −2. It is 10 g / g or more.
以下、本発明に係る感放射線性樹脂組成物について説明する。
アルカリ不溶性またはアルカリ難溶性であって酸の作用によりアルカリ易溶性となる酸解離性基含有樹脂(A)は、下記式(1−1)で表される繰り返し単位(1−1)と式(1−2)で表される繰り返し単位(1−2)とを含有することが好ましい。
The acid-dissociable group-containing resin (A) that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid has a repeating unit (1-1) represented by the following formula (1-1) and a formula ( It is preferable to contain the repeating unit (1-2) represented by 1-2).
ここで、以下で用いる多環型の脂環式骨格の名称に関して命名根拠を下式(命名)に示す。
上記式(1−2)中のR2としては、例えばビシクロ[2.2.1]ヘプタン、トリシクロ[5.2.1.02,6]デカン、テトラシクロ[6.2.1.13,6.02,7]ドデカン、アダマンタン、シクロペンタン、シクロヘキサン等のシクロアルカン類等に由来する脂環族環からなる基;これら脂環族環からなる基を例えば、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、2−メチルプロピル基、1−メチルプロピル基、t−ブチル基等の炭素数1〜4の直鎖状、分岐状または環状のアルキル基の1種以上あるいは1個以上で置換した基等が挙げられる。 The R 2 in the above formula (1-2), for example, bicyclo [2.2.1] heptane, tricyclo [5.2.1.0 2,6] decane, tetracyclo [6.2.1.1 3 , 6 . 0 2,7 ] a group consisting of an alicyclic ring derived from cycloalkanes such as dodecane, adamantane, cyclopentane, cyclohexane, etc .; a group consisting of these alicyclic rings is, for example, methyl group, ethyl group, n-propyl A linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. The above or a group substituted with one or more may be mentioned.
また、R2の1価または2価の脂環式炭化水素基の誘導体としては、例えば、ヒドロキシル基;カルボキシル基;オキソ基(即ち、=O基);ヒドロキシメチル基、1−ヒドロキシエチル基、2−ヒドロキシエチル基、1−ヒドロキシプロピル基、2−ヒドロキシプロピル基、3−ヒドロキシプロピル基、2−ヒドロキシブチル基、3−ヒドロキシブチル基、4−ヒドロキシブチル基等の炭素数1〜4のヒドロキシアルキル基;メトキシ基、エトキシ基、n−プロポキシ基、i−プロポキシ基、n−ブトキシ基、2−メチルプロポキシ基、1−メチルプロポキシ基、t−ブトキシ基等の炭素数1〜4のアルコキシル基;シアノ基;シアノメチル基、2−シアノメチル基、3−シアノプロピル基、4−シアノブチル基等の炭素数2〜5のシアノアルキル基等の置換基を1種以上あるいは1個以上有する基が挙げられる。
これらの置換基のうち、ヒドロキシル基、カルボキシル基、ヒドロキシメチル基、シアノ基、シアノメチル基等が好ましい。
Examples of the derivative of R 2 monovalent or divalent alicyclic hydrocarbon group include, for example, hydroxyl group; carboxyl group; oxo group (ie, ═O group); hydroxymethyl group, 1-hydroxyethyl group, C1-C4 hydroxy such as 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. Alkyl group; alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group Cyano group; C 2-5 cyano such as cyanomethyl group, 2-cyanomethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. A group having a substituent such as alkyl group one or more or one or more.
Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group, and the like are preferable.
また、R2の炭素数1〜4の直鎖状もしくは分岐状のアルキル基としては、例えば、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、2−メチルプロピル基、1−メチルプロピル基、t−ブチル基等が挙げられる。
これらのアルキル基のうち、メチル基、エチル基、n−プロピル基、i−プロピル基が好ましい。
式(1−2)中の−C(R2)3を形成する官能基側鎖として好ましいものを挙げると、1−メチル−1−シクロペンチル基、1−エチル−1−シクロペンチル基、1−メチル−1−シクロヘキシル基、1−エチル−1−シクロヘキシル基、2−メチルアダマンタン−2−イル基、2−メチル−3−ヒドロキシアダマンタン−2−イル基、2−エチルチルアダマンタン−2−イル基、2−エチル−3−ヒドロキシアダマンタン−2−イル基、2−n−プロピルアダマンタン−2−イル基、2−n−プロピル−3−ヒドロキシアダマンタン−2−イル基、2−イソプロピルアダマンタン−2−イル基、2−イソプロピル−3−ヒドロキシアダマンタン−2−イル基、2−メチルビシクロ[2.2.1]ヘプト−2−イル基、2−エチルビシクロ[2.2.1]ヘプト−2−イル基、8−メチルトリシクロ[5.2.1.02,6]デカ−8−イル基、8−エチルトリシクロ[5.2.1.02,6]デカ−8−イル基、4−メチル−テトラシクロ[6.2.1.13,6.02,7]ドデカ−4−イル基、4−エチル−テトラシクロ[6.2.1.13,6.02,7]ドデカ−4−イル基、1−(ビシクロ[2.2.1]ヘプト−2−イル)−1−メチルエチル基、1−(トリシクロ[5.2.1.02,6]デカ−8−イル)−1−メチルエチル基、1−(テトラシクロ[6.2.1.13,6.02,7]デカ−4−イル)−1−メチルエチル基、1−(アダマンタン−1−イル)−1−メチルエチル基、1−(3−ヒドロキシアダマンタン−1−イル)−1−メチルエチル基、1,1−ジシクロヘキシルエチル基、1,1−ジ(ビシクロ[2.2.1]ヘプト−2−イル)エチル基、1,1−ジ(トリシクロ[5.2.1.02,6]デカ−8−イル)エチル基、1,1−ジ(テトラシクロ[6.2.1.13,6.02,7]ドデカ−4−イル)エチル基、1,1−ジ(アダマンタン−1−イル)エチル基等が挙げられる。
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R 2 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable.
Preferred examples of the functional group side chain forming -C (R 2 ) 3 in formula (1-2) include 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl -1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyladamantan-2-yl group, 2-methyl-3-hydroxyadamantan-2-yl group, 2-ethyltyladamantan-2-yl group, 2-ethyl-3-hydroxyadamantan-2-yl group, 2-n-propyladamantan-2-yl group, 2-n-propyl-3-hydroxyadamantan-2-yl group, 2-isopropyladamantan-2-yl group Group, 2-isopropyl-3-hydroxyadamantan-2-yl group, 2-methylbicyclo [2.2.1] hept-2-yl group, 2-ethylbicyclo 2.2.1] hept-2-yl group, 8-methyltricyclo [5.2.1.0 2, 6] dec-8-yl group, 8-ethyl-tricyclo [5.2.1.0 2,6 ] dec-8-yl group, 4-methyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-yl group, 4-ethyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-yl group, 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl group, 1- (tricyclo [5.2.1.0 2, 6 ] dec-8-yl) -1-methylethyl group, 1- (tetracyclo [6.2.1.1 3,6 .0 2,7 ] dec-4-yl) -1-methylethyl group, 1 -(Adamantan-1-yl) -1-methylethyl group, 1- (3-hydroxyadamantan-1-yl) -1-methylethyl group, 1,1-dicyclohexylethyl group, 1,1-di (bicyclo [ 2.2.1] Hept-2-yl) ethyl group, 1,1-di (tricyclo [5.2.1.0 2,6 ] dec-8-yl) ethyl group, 1,1-di (tetracyclo) [6.2.1.1 3,6 .0 2,7] dodeca-4-yl) ethyl group, 1,1-di (adamantan-1-yl) ethyl group, And the like.
式(2−1)中のX1およびX2のうちアルキル基としては、メチル基、エチル基、n−プロピル基、n−ブチル基等が挙げられる。フッ素化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基等が挙げられる。
式(2−2)におけるR3、式(2−3)におけるR4、式(2−4)におけるR5において、炭素数1〜4の直鎖状もしくは分岐状アルキル基としては、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、t−ブチル基等が挙げられる。また、炭素数1〜4の直鎖状もしくは分岐状アルコキシル基としては、メトキシ基、エトキシ基、n−プロポキシ基、i−プロポキシ基、n−ブトキシ基、t−ブトキシ基等が挙げられる。
Of X 1 and X 2 in formula (2-1), examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the fluorinated alkyl group include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.
In R 3 in Formula (2-2), R 4 in Formula (2-3), and R 5 in Formula (2-4), the linear or branched alkyl group having 1 to 4 carbon atoms is a methyl group. , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group and the like. Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group.
繰り返し単位(1−1)を与える単量体の中で好ましいものとしては、(メタ)アクリル酸(1,1,1−トリフルオロ−2−トリフルオロメチル−2−ヒドロキシ−3−プロピル)エステル、(メタ)アクリル酸(1,1,1−トリフルオロ−2−トリフルオロメチル−2−ヒドロキシ−4−ブチル)エステル、(メタ)アクリル酸(1,1,1−トリフルオロ−2−トリフルオロメチル−2−ヒドロキシ−5−ペンチル)エステル、(メタ)アクリル酸(1,1,1−トリフルオロ−2−トリフルオロメチル−2−ヒドロキシ−4−ペンチル)エステル、(メタ)アクリル酸2−{[5−(1',1',1'−トリフルオロ−2'−トリフルオロメチル−2'−ヒドロキシ)プロピル]ビシクロ[2.2.1]ヘプチル}エステル、(メタ)アクリル酸3−{[8−(1',1',1'−トリフルオロ−2'−トリフルオロメチル−2'−ヒドロキシ)プロピル] テトラシクロ[6.2.1.13,6.02,7]ドデシル}エステル、(メタ)アクリル酸−5−オキソー4−オキサートリシクロ[4.2.1.03,7]ノナー2−イルエステル、(メタ)アクリル酸−7−オキソー6−オキサービシクロ[3.2.1]オクター4−イルエステル、(メタ)アクリル酸−2−オキソテトラヒドロピラン−4−イルエステル、(メタ)アクリル酸−4−メチルー2−オキソテトラヒドロピラン−4−イルエステル、(メタ)アクリル酸−5−オキソテトラヒドロフラン−3−イルエステル、(メタ)アクリル酸−2−オキソテトラヒドロフランー3−イルエステル、(メタ)アクリル酸−5−オキソテトラヒドロフラン−2−イルメチルエステル、(メタ)アクリル酸−3,3−ジメチル−5−オキソテトラヒドロフラン−2−イルメチルエステル等が挙げられる。 Among the monomers that give the repeating unit (1-1), (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester is preferable. , (Meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-tri Fluoromethyl-2-hydroxy-5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2 -{[5- (1 ', 1', 1'-trifluoro-2'-trifluoromethyl-2'-hydroxy) propyl] bicyclo [2.2.1] heptyl} ester, (meth) acrylic acid 3-{[8- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodecyl} ester, (meth) acrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 3,7 ] noner 2-yl ester, (meth) acrylic acid-7- Oxo-6-oxabicyclo [3.2.1] oct-4-yl ester, (meth) acrylic acid-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran -4-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-2 -Ylmethyl ester, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester Etc.
繰り返し単位(1−2)を与える単量体の中で好ましいものとしては、(メタ)アクリル酸2−メチルアダマンチル−2−イルエステル、(メタ)アクリル酸2−メチル−3−ヒドロキシアダマンタン−2−イルエステル、(メタ)アクリル酸2−エチルアダマンタン−2−イルエステル、(メタ)アクリル酸2−エチル−3−ヒドロキシアダマンタン−2−イルエステル、(メタ)アクリル酸2−n−プロピルアダマンタン−2−イルエステル、(メタ)アクリル酸2−イソプロピルアダマンタン−2−イルエステル、(メタ)アクリル酸−2−メチルビシクロ[2.2.1]ヘプト−2−イルエステル、(メタ)アクリル酸−2−エチルビシクロ[2.2.1]ヘプト−2−イルエステル、(メタ)アクリル酸−8−メチルトリシクロ[5.2.1.02,6]デカン−8−イルエステル、(メタ)アクリル酸−8−エチルトリシクロ[5.2.1.02,6]デカン−8−イルエステル、(メタ)アクリル酸−4−メチルテトラシクロ[6.2.13,6.02,7]ドデカン−4−イルエステル、(メタ)アクリル酸−4−エチルテトラシクロ[6.2.13,6.02,7]ドデカン−4−イルエステル、(メタ)アクリル酸1−(ビシクロ[2.2.1]ヘプト−2−イル)−1−メチルエチルエステル、(メタ)アクリル酸1−(トリシクロ[5.2.1.02,6]デカン−8−イル)−1−メチルエチルエステル、(メタ)アクリル酸1−(テトラシクロ[6.2.13,6.02,7]ドデカン−4−イル)−1−メチルエチルエステル、(メタ)アクリル酸1−(アダマンタン−1−イル)−1−メチルエチルエステル、(メタ)アクリル酸1−(3−ヒドロキシアダマンタン−1−イル)−1−メチルエチルエステル、(メタ)アクリル酸1,1−ジシクロヘキシルエチルエステイル、(メタ)アクリル酸1,1−ジ(ビシクロ[2.2.1]ヘプト−2−イル)エチルエステル、(メタ)アクリル酸1,1−ジ(トリシクロ[5.2.1.02,6]デカン−8−イル)エチルエステル、(メタ)アクリル酸1,1−ジ(テトラシクロ[6.2.13,6.02,7]ドデカン−4−イル)エチルエステル、(メタ)アクリル酸1,1−ジ(アダマンタン−1−イル)エチルエステル、(メタ)アクリル酸1−メチル−1−シクロペンチルエステル、(メタ)アクリル酸1−エチル−1−シクロペンチルエステル、(メタ)アクリル酸1−メチル−1−シクロヘキシルエステル、(メタ)アクリル酸1−エチル−1−シクロヘキシルエステル等が挙げられる。 Among the monomers that give the repeating unit (1-2), (meth) acrylic acid 2-methyladamantyl-2-yl ester, (meth) acrylic acid 2-methyl-3-hydroxyadamantane-2 are preferable. -Yl ester, (meth) acrylic acid 2-ethyladamantan-2-yl ester, (meth) acrylic acid 2-ethyl-3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-n-propyladamantane- 2-yl ester, (meth) acrylic acid 2-isopropyladamantan-2-yl ester, (meth) acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid- 2-Ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-8-methyltricyclo [ .2.1.0 2,6] decan-8-yl ester, (meth) ethyl-8-acrylic acid tricyclo [5.2.1.0 2,6] decan-8-yl ester, (meth) 4-methyltetracycloacrylic acid [6.2.1 3,6 . 0 2,7 ] dodecan-4-yl ester, (meth) acrylic acid-4-ethyltetracyclo [6.2.1 3,6 . 0 2,7 ] dodecan-4-yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl ester, (meth) acrylic acid 1- (tricyclo [5.2.1.02,6] decan-8-yl) -1-methylethyl ester, (meth) acrylic acid 1- (tetracyclo [6.2.1 3,6 .0 2,7 ] dodecane- 4-yl) -1-methylethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester, (meth) acrylic acid 1- (3-hydroxyadamantan-1-yl)- 1-methylethyl ester, (meth) acrylic acid 1,1-dicyclohexylethyl ester, (meth) acrylic acid 1,1-di (bicyclo [2.2.1] hept-2-yl) ethyl ester, (meth Acry 1,1-di (tricyclo [5.2.1.0 2,6] decan-8-yl) ethyl ester, (meth) acrylic acid 1,1-di (tetracyclo [6.2.1 3,6 .0 2,7] dodecane-4-yl) ethyl ester, (meth) acrylic acid 1,1-di (adamantan-1-yl) ethyl ester, (meth) acrylic acid 1-methyl-1-cyclopentyl ester, ( Examples include (meth) acrylic acid 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-cyclohexyl ester, (meth) acrylic acid 1-ethyl-1-cyclohexyl ester, and the like.
繰り返し単位(1−2)を与える単量体の中で、特に好適な単量体としては、(メタ)アクリル酸2−メチルアダマンタン−2−イルエステル、(メタ)アクリル酸2−エチルアダマンタン−2−イルエステル、(メタ)アクリル酸−2−メチルビシクロ[2.2.1]ヘプト−2−イルエステル、(メタ)アクリル酸−2−エチルビシクロ[2.2.1]ヘプト−2−イルエステル、(メタ)アクリル酸1−(ビシクロ[2.2.1]ヘプト−2−イル)−1−メチルエチルエステル、(メタ)アクリル酸1−(アダマンタン−1−イル)−1−メチルエチルエステル、(メタ)アクリル酸1−メチル−1−シクロペンチルエステル、(メタ)アクリル酸1−エチル−1−シクロペンチルエステル、(メタ)アクリル酸1−メチル−1−シクロヘキシルエステル、(メタ)アクリル酸1−エチル−1−シクロヘキシルエステル等が挙げられる。 Among the monomers giving the repeating unit (1-2), particularly preferred monomers are (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-ethyladamantane- 2-yl ester, (meth) acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl Yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methyl Ethyl ester, (meth) acrylic acid 1-methyl-1-cyclopentyl ester, (meth) acrylic acid 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-silane B hexyl ester, and (meth) acrylic acid 1-ethyl-1-cyclohexyl ester.
樹脂(A)は、上記繰り返し単位(1−1)、(1−2)以外にさらに他の繰り返し単位を含むことができる。他の繰り返し単位を与える単量体としては、例えば(メタ)アクリル酸3−ヒドロキシアダマンタン−1−イルエステル、(メタ)アクリル酸3、5−ジヒドロキシアダマンタン−1−イルエステル、(メタ)アクリル酸3−シアノアダマンタン−1−イルエステル、(メタ)アクリル酸3−カルボキシルアダマンタン−1−イルエステル、(メタ)アクリル酸3、5−ジカルボキシルアダマンタン−1−イルエステル、(メタ)アクリル酸3−カルボキシル−5−ヒドロキシアダマンタン−1−イルエステル、(メタ)アクリル酸3−メトキシカルボニル−5−ヒドロキシアダマンタン−1−イルエステル、(メタ)アクリル酸、(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、クロトンアミド、マレインアミド、フマルアミド、メサコンアミド、シトラコンアミド、イタコンアミド等の不飽和アミド化合物;メチレングリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、2,5−ジメチル−2,5−ヘキサンジオールジ(メタ)アクリレート、1,2−アダマンタンジオールジ(メタ)アクリレート、1,3−アダマンタンジオールジ(メタ)アクリレート、1,4−アダマンタンジオールジ(メタ)アクリレート、トリシクロデカニルジメチロールジ(メタ)アクリレート等の多官能性単量体等が挙げられる。 Resin (A) can contain another repeating unit in addition to the repeating units (1-1) and (1-2). Examples of monomers that give other repeating units include (meth) acrylic acid 3-hydroxyadamantan-1-yl ester, (meth) acrylic acid 3, 5-dihydroxyadamantan-1-yl ester, and (meth) acrylic acid. 3-cyanoadamantan-1-yl ester, (meth) acrylic acid 3-carboxyladamantan-1-yl ester, (meth) acrylic acid 3, 5-dicarboxyladamantan-1-yl ester, (meth) acrylic acid 3- Carboxyl-5-hydroxyadamantan-1-yl ester, (meth) acrylic acid 3-methoxycarbonyl-5-hydroxyadamantan-1-yl ester, (meth) acrylic acid, (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide, crotonamide, maleamide, fu Unsaturated amide compounds such as luamide, mesaconamide, citraconic amide, itaconic amide; methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, etc. A functional monomer etc. are mentioned.
樹脂(A)は、上記繰り返し単位(1−1)、繰り返し単位(1−2)で構成することが好ましい。、繰り返し単位(1−1)および繰り返し単位(1−2)の配合割合は、全繰り返し単位に対して、繰り返し単位(1−1)が20〜70モル%、好ましくは30〜60モル%;繰り返し単位(1−2)が10〜60モル%、好ましくは10〜50モル%である。
繰り返し単位(1−1)の含有率が、20モル%未満では、レジストとしての現像性および解像性が低下する傾向にあり、その含有率が70モル%をこえるとレジスト溶媒への溶解性が低下する傾向にある。繰り返し単位(1−2)の含有率が、10モル%未満では、レジストとしての解像性が劣化する傾向にあり、含有率が60モル%をこえるとレジストとしての現像性が低下する傾向にある。また、その他の繰り返し単位を含有でき、含有量は通常50モル%以下、好ましくは30モル%以下である。
The resin (A) is preferably composed of the repeating unit (1-1) and the repeating unit (1-2). The blending ratio of the repeating unit (1-1) and the repeating unit (1-2) is 20 to 70 mol%, preferably 30 to 60 mol% of the repeating unit (1-1) with respect to all repeating units; The repeating unit (1-2) is 10 to 60 mol%, preferably 10 to 50 mol%.
When the content of the repeating unit (1-1) is less than 20 mol%, the developability and resolution as a resist tend to be lowered. When the content exceeds 70 mol%, the solubility in a resist solvent is increased. Tend to decrease. When the content of the repeating unit (1-2) is less than 10 mol%, the resolution as a resist tends to deteriorate, and when the content exceeds 60 mol%, the developability as a resist tends to decrease. is there. Moreover, another repeating unit can be contained and content is 50 mol% or less normally, Preferably it is 30 mol% or less.
樹脂(A)は、例えば、各繰り返し単位に対応する単量体の混合物を、ヒドロパーオキシド類、ジアルキルパーオキシド類、ジアシルパーオキシド類、アゾ化合物等のラジカル重合開始剤を使用し、必要に応じて連鎖移動剤の存在下、適当な溶媒中で重合することにより製造することができる。
上記重合に使用される溶媒としては、例えば、シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン類;酢酸エチル、酢酸n−ブチル、酢酸i−ブチル、プロピオン酸メチル、プロピレングリコールモノメチルエーテルアセテート等の飽和カルボン酸エステル類;γ−ブチロラクトン等のアルキルラクトン類;テトラヒドロフラン、ジメトキシエタン類、ジエトキシエタン類等のエーテル類;2−ブタノン、2−ヘプタノン、メチルイソブチルケトン等のアルキルケトン類;シクロヘキサノン等のシクロアルキルケトン類;2−プロパノール、プロピレングリコールモノメチルエーテル等のアルコール類等を挙げることができる。
これらの溶媒は、単独でまたは2種以上を混合して使用することができる。また、重合における反応温度は、通常、40〜120℃、好ましくは50〜100℃であり、反応時間は、通常、1〜48時間、好ましくは1〜24時間である。
Resin (A) is, for example, a mixture of monomers corresponding to each repeating unit, using a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc. Accordingly, it can be produced by polymerization in an appropriate solvent in the presence of a chain transfer agent.
Examples of the solvent used for the polymerization include cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, propylene glycol monomethyl ether. Saturated carboxylic acid esters such as acetate; alkyl lactones such as γ-butyrolactone; ethers such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes; alkyl ketones such as 2-butanone, 2-heptanone and methyl isobutyl ketone; Examples thereof include cycloalkyl ketones such as cyclohexanone; alcohols such as 2-propanol and propylene glycol monomethyl ether.
These solvents can be used alone or in admixture of two or more. Moreover, the reaction temperature in superposition | polymerization is 40-120 degreeC normally, Preferably it is 50-100 degreeC, and reaction time is 1-48 hours normally, Preferably it is 1-24 hours.
本発明における樹脂(A)は、ハロゲン、金属等の不純物が少ないのは当然のことながら、残留単量体やオリゴマー成分が既定値以下、例えばHPLCで0.1重量%等、であることが好ましく、それにより、レジストとしての感度、解像度、プロセス安定性、パターン形状等をさらに改善することができるだけでなく、液中異物や感度等の経時変化がないレジストを提供できる。
樹脂(A)の精製法としては、例えば、以下の方法が挙げられる。金属等の不純物を除去する方法としては、ゼータ電位フィルターを用いて樹脂溶液中の金属を吸着させる方法や蓚酸やスルホン酸等の酸性水溶液で樹脂溶液を洗浄することで金属をキレート状態にして除去する方法等が挙げられる。また、残留単量体やオリゴマー成分を規定値以下に除去する方法としては、水洗や適切な溶媒を組み合わせることにより残留単量体やオリゴマー成分を除去する液々抽出法、特定の分子量以下のもののみを抽出除去する限外濾過等の溶液状態での精製方法や、樹脂溶液を貧溶媒へ滴下することで樹脂を貧溶媒中に凝固させることにより残留単量体等を除去する再沈澱法や濾別した樹脂スラリー貧溶媒で洗浄する等の固体状態での精製方法が有る。また、これらの方法を組み合わせることもできる。
上記再沈澱法に用いられる貧溶媒としては、精製する樹脂の物性等に左右され一概には例示することはできない。適宜、貧溶媒は選定されるものである。
The resin (A) in the present invention is naturally low in impurities such as halogen and metal, and the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by weight by HPLC. Preferably, this not only can further improve the sensitivity, resolution, process stability, pattern shape, and the like as a resist, but also can provide a resist that does not change with time such as foreign matter in liquid or sensitivity.
Examples of the purification method of the resin (A) include the following methods. As a method of removing impurities such as metals, the metal is chelated and removed by adsorbing the metal in the resin solution using a zeta potential filter or by washing the resin solution with an acidic aqueous solution such as oxalic acid or sulfonic acid. And the like. In addition, as a method of removing residual monomer and oligomer components below the specified value, a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water washing and an appropriate solvent, those having a specific molecular weight or less A purification method in a solution state such as ultrafiltration that only extracts and removes, and a reprecipitation method that removes residual monomers by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, There is a purification method in a solid state such as washing with a resin slurry poor solvent separated by filtration. Moreover, these methods can also be combined.
The poor solvent used in the reprecipitation method depends on the physical properties of the resin to be purified and cannot be generally exemplified. As appropriate, the poor solvent is selected.
樹脂(A)のゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算重量平均分子量(以下、「Mw」という。)は、通常、1,000〜300,000、好ましくは2,000〜200,000、さらに好ましくは3,000〜100,000である。この場合、樹脂(A)のMwが1,000未満では、レジストとしての耐熱性が低下する傾向があり、一方300,000をこえると、レジストとしての現像性が低下する傾向がある。
また、樹脂(A)のMwとゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算数平均分子量(以下、「Mn」という。)との比(Mw/Mn)は、通常、1〜5、好ましくは1〜3である。本発明において、樹脂(A)は、単独でまたは2種以上を混合して使用できる。
The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the resin (A) is usually 1,000 to 300,000, preferably 2,000 to 200,000, More preferably, it is 3,000-100,000. In this case, if the Mw of the resin (A) is less than 1,000, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease.
The ratio (Mw / Mn) of Mw of the resin (A) to polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) by gel permeation chromatography (GPC) is usually 1 to 5, preferably 1-3. In this invention, resin (A) can be used individually or in mixture of 2 or more types.
樹脂(A)は、上記特性に加えて上述した動的光散乱法による測定の結果、後述するレジスト溶剤(C)溶液の樹脂濃度変化に伴う係数(kD)が−2.20g/g以上、好ましくは−2.10g/g以上あることが必要であり、樹脂(A)を2種以上混合して使用する場合は、少なくとも1種が上記範囲になることが必要である。動的光散乱法を用いることにより、感放射線性樹脂(A)の微小な解像性や溶解性の僅かな相違点が評価でき、係数(kD)が−2.20g/g以上あることにより、従来のレジスト性能を維持したまま、現像欠陥を発生することがない優れた感放射線性樹脂組成物が得られる。また、樹脂(A)を2種以上混合して使用する場合は、上記特性を有する樹脂が少なくとも1重量%以上、好ましくは5重量%以上含有することが好ましい。 Resin (A) has a coefficient (k D ) of −2.20 g / g or more as a result of measurement by the above-described dynamic light scattering method in addition to the above characteristics, as a result of a resin concentration change in a resist solvent (C) solution described later. In addition, it is necessary to be −2.10 g / g or more, and when two or more kinds of resins (A) are mixed and used, it is necessary that at least one kind falls within the above range. By using the dynamic light scattering method, slight differences in the resolution and solubility of the radiation-sensitive resin (A) can be evaluated, and the coefficient (k D ) is −2.20 g / g or more. Thus, an excellent radiation-sensitive resin composition that does not generate development defects while maintaining the conventional resist performance can be obtained. Moreover, when using 2 or more types of resin (A) in mixture, it is preferable that the resin which has the said characteristic contains at least 1 weight% or more, Preferably it contains 5 weight% or more.
レジスト溶剤(B)
本発明で使用できるレジスト溶剤(B)は特に限定されるものではないが、上記樹脂(A)を溶解させること、沸点が約150℃以上あること、および樹脂溶液塗布時にハレーションを発生させないことの3つの条件を満たすレジスト溶剤であることが好ましい。
好ましいレジスト溶剤(B)としては、2−ヘキサノン、2−ヘプタノン、2−オクタノン、シクロペンタノン、シクロヘキサノン、プロピレングリコールモノメ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、2−ヒドロキシプロピオン酸メチル、2−ヒドロキシプロピオン酸エチル、3−メトキシプロピオン酸メチル、3−メトキシプロピオン酸エチル、3−エトキシプロピオン酸メチル、3−エトキシプロピオン酸エチル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、エチレングリコールモノメチルエーテルアセテート、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メチルエーテル、プロピレングリコールモノエチルエーテル、酢酸n−ブチル、ピルビン酸メチル、ピルビン酸エチル、N−メチルピロリドン、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、γ−ブチロラクトン等が挙げられる。
これらの溶剤は、単独でまたは2種以上を混合して使用できるが、例中、2−ヘプタノン、シクロヘキサノン、プロピレングリコールモノメチルエーテルアセテート、2−ヒドロキシプロピオン酸エチル、3−エトキシプロピオン酸エチル、プロピレングリコールモノメチルエーテル、γ−ブチロラクトン等が好ましい。
Resist solvent (B)
The resist solvent (B) that can be used in the present invention is not particularly limited, but it is possible to dissolve the resin (A), to have a boiling point of about 150 ° C. or higher, and not to generate halation when the resin solution is applied. A resist solvent that satisfies the three conditions is preferred.
Preferred resist solvents (B) include 2-hexanone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-hydroxypropionate, 2-hydroxy Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate n- butyl, methyl pyruvate, ethyl pyruvate, N- methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, .gamma.-butyrolactone.
These solvents can be used alone or in admixture of two or more. In the examples, 2-heptanone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, propylene glycol Monomethyl ether, γ-butyrolactone and the like are preferable.
感放射線性樹脂組成物は、上記樹脂(A)を酸解離性基含有樹脂として用い、放射線の照射により酸を発生する成分である酸発生剤(C)と組み合わせることにより得られる。
感放射線性酸発生剤(C)として好ましいものとしては、
トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、トリフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、トリフェニルスルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、トリフェニルスルホニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、トリフェニルスルホニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、トリフェニルスルホニウムカンファースルホネート、
The radiation-sensitive resin composition is obtained by using the resin (A) as an acid-dissociable group-containing resin and combining with an acid generator (C) that is a component that generates an acid upon irradiation with radiation.
As a preferred radiation sensitive acid generator (C),
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1, 1,2,2-tetrafluoroethane sulfonate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.1 2,5 .1, 7,10 ] dodecanyl) -1,1-difluoroethane sulfonate, triphenylsulfonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate,
4−シクロヘキシルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、4−シクロヘキシルフェニルジフェニルスルホニウムカンファースルホネート、 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7, 10] dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N-bis (nonafluoro -n- butanesulfonyl) imidate, 4-sik Hexylphenyl camphorsulfonate,
4−t−ブチルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、4−t−ブチルフェニルジフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、4−t−ブチルフェニルジフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、4−t−ブチルフェニルジフェニルスルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、4−t−ブチルフェニルジフェニルスルホニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、4−t−ブチルフェニルジフェニルスルホニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、4−t−ブチルフェニルジフェニルスルホニウムカンファースルホネート、
トリ(4−t−ブチルフェニル)スルホニウムトリフルオロメタンスルホネート、トリ(4−t−ブチルフェニル)スルホニウムノナフルオロ−n−ブタンスルホネート、トリ(4−t−ブチルフェニル)スルホニウムパーフルオロ−n−オクタンスルホネート、トリ(4−t−ブチルフェニル)スルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、トリ(4−t−ブチルフェニル)スルホニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、トリ(4−t−ブチルフェニル)スルホニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、トリ(4−t−ブチルフェニル)スルホニウムカンファースルホネート、
4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 4-t-butyl Phenyldiphenyl Sulfo camphorsulfonate,
Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N-bis (nonafluoro - n-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfonium carbonate Far sulfonate,
ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ−n−ブタンスルホネート、ジフェニルヨードニウムパーフルオロ−n−オクタンスルホネート、ジフェニルヨードニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、ジフェニルヨードニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、ジフェニルヨードニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、ジフェニルヨードニウムカンファースルホネート、
ビス(4−t−ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムノナフルオロ−n−ブタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムパーフルオロ−n−オクタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、ビス(4−t−ブチルフェニル)ヨードニウムカンファースルホネート、
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N-bis ( Nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate,
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N-bis (nonafluoro - n-butanesulfonyl) imidate, bis (4-t-butylphenyl) iodonium Far sulfonate,
1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネート、1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウムパーフルオロ−n−オクタンスルホネート、1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウムカンファースルホネート、 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4 n- butoxy naphthalen-1-yl) tetrahydrothiophenium N, N-bis (nonafluoro -n- butanesulfonyl) imidate, 1- (4-n- butoxy-naphthalene-1-yl) tetrahydrothiophenium camphorsulfonate,
1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムパーフルオロ−n−オクタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウム2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムN,N−ビス(ノナフルオロ−n−ブタンスルホニル)イミデート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムカンファースルホネート、 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethane scan Phonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydro Thiophenium camphorsulfonate,
N−(トリフルオロメタンスルホニルオキシ)スクシンイミド、N−(ノナフルオロ−n−ブタンスルホニルオキシ)スクシンイミド、N−(パーフルオロ−n−オクタンスルホニルオキシ)スクシンイミド、N−(2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホニルオキシ)スクシンイミド、N−(2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホニルオキシ)スクシンイミド、N−(カンファースルホニルオキシ)スクシンイミド、 N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, N- (2- (3-tetracyclo [4.4.0.1 2,5 .1, 7,10 ] dodecanyl) -1,1-difluoroethanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide,
N−(トリフルオロメタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(ノナフルオロ−n−ブタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(パーフルオロ−n−オクタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(カンファースルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、等が挙げられる。 N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept -5 -D 2,3-dicarboximide, N- (camphorsulfonyloxy oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and the like.
本発明において、感放射線性酸発生剤(C)は、単独でまたは2種以上を混合して使用できる。感放射線性酸発生剤(C)の使用量は、レジストとしての感度および現像性を確保する観点から、樹脂(A)100重量部に対して、通常、0.1〜20重量部、好ましくは0.1〜7重量部である。この場合、感放射線性酸発生剤(C)の使用量が0.1重量部未満では、感度および現像性が低下する傾向があり、一方10重量部をこえると、放射線に対する透明性が低下して、矩形のレジストパターンを得られ難くなる傾向がある。 In this invention, a radiation sensitive acid generator (C) can be used individually or in mixture of 2 or more types. The amount of the radiation sensitive acid generator (C) used is usually 0.1 to 20 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the resin (A), from the viewpoint of securing the sensitivity and developability as a resist. 0.1 to 7 parts by weight. In this case, if the amount of the radiation-sensitive acid generator (C) used is less than 0.1 parts by weight, the sensitivity and developability tend to decrease. On the other hand, if it exceeds 10 parts by weight, the transparency to radiation decreases. Therefore, it tends to be difficult to obtain a rectangular resist pattern.
本発明の感放射線性樹脂組成物には、露光により感放射線性酸発生剤(C)から生じる酸のレジスト被膜中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する作用を有する酸拡散制御剤(F)を配合することが好ましい。酸拡散制御剤(F)を配合することにで、感放射線性樹脂組成物の貯蔵安定性やレジストとしての解像度がさらに向上するとともに、露光から現像処理までの引き置き時間(PED)の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた組成物が得られる。
酸拡散制御剤(F)としては、レジストパターンの形成工程中の露光や加熱処理により塩基性が変化しない含窒素有機化合物が好ましい。このような含窒素有機化合物としては、「3級アミン化合物」、「アミド基含有化合物」、「4級アンモニウムヒドロキシド化合物」、「含窒素複素環化合物」等が挙げられる。
The radiation-sensitive resin composition of the present invention has the effect of controlling the diffusion phenomenon in the resist film of the acid generated from the radiation-sensitive acid generator (C) by exposure and suppressing undesirable chemical reactions in the non-exposed areas. It is preferable to mix the acid diffusion controlling agent (F) having. By blending the acid diffusion control agent (F), the storage stability of the radiation-sensitive resin composition and the resolution as a resist are further improved, and due to fluctuations in the holding time (PED) from exposure to development processing. A change in the line width of the resist pattern can be suppressed, and a composition having excellent process stability can be obtained.
The acid diffusion controller (F) is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern formation step. Examples of such nitrogen-containing organic compounds include “tertiary amine compounds”, “amide group-containing compounds”, “quaternary ammonium hydroxide compounds”, “nitrogen-containing heterocyclic compounds”, and the like.
「3級アミン化合物」としては、例えば、トリエチルアミン、トリ−n−プロピルアミン、トリ−n−ブチルアミン、トリ−n−ペンチルアミン、トリ−n−ヘキシルアミン、トリ−n−ヘプチルアミン、トリ−n−オクチルアミン、トリ−n−デシルアミン、シクロヘキシルジメチルアミン、ジシクロヘキシルメチルアミン、トリシクロヘキシルアミン等のトリ(シクロ)アルキルアミン類;N,N−ジメチルアニリン、2,6−ジメチルアニリン、2,6−ジイソプロピルアニリン等の芳香族アミン類;トリエタノールアミン、ジエタノールアニリンなどのアルカノールアミン類;N,N,N',N'−テトラキス(2−ヒドロキシプロピル)エチレンジアミン、ビス(2−ジメチルアミノエチル)エーテル、ビス(2−ジエチルアミノエチル)エーテル等が挙げられる。 Examples of the “tertiary amine compound” include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n. -Tri (cyclo) alkylamines such as octylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; N, N-dimethylaniline, 2,6-dimethylaniline, 2,6-diisopropyl Aromatic amines such as aniline; alkanolamines such as triethanolamine and diethanolaniline; N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, bis (2-dimethylaminoethyl) ether, bis (2-Diethylaminoe Le) ether and the like.
「アミド基含有化合物」としては、例えば、N−t−ブトキシカルボニルジ−n−オクチルアミン、N−t−ブトキシカルボニルジシクロヘキシルアミン、N−t−ブトキシカルボニル−1−アダマンチルアミン、N−t−ブトキシカルボニル−N−メチル−1−アダマンチルアミン、N−t−ブトキシカルボニル−4,4'−ジアミノジフェニルメタン、N−t−ブトキシカルボニルピロリジン、N−t−ブトキシカルボニル−4−ヒペリジン、N−t−ブトキシカルボニルアミノ−1−アダマンタン、N−t−ブトキシカルボニルアミノ−2−アダマンタン、N−t−ブトキシカルボニルベンズイミダゾール、N−t−ブトキシカルボニル−2−メチルベンズイミダゾール、N−t−ブトキシカルボニル−2−フェニルベンズイミダゾール等のN−t−ブトキシカルボニル基含有アミノ化合物;ホルムアミド、N−メチルホルムアミド、N,N−ジメチルホルムアミド、アセトアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、プロピオンアミド、ベンズアミド、ピロリドン、N−メチルピロリドン等が挙げられる。 Examples of the “amide group-containing compound” include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxy. Carbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl-4-hyperidine, Nt-butoxy Carbonylamino-1-adamantane, Nt-butoxycarbonylamino-2-adamantane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2- Phenylbenzimidazole Nt-butoxycarbonyl group-containing amino compounds such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methyl pyrrolidone.
「4級アンモニウムヒドロキシド化合物」としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ−n−プロピルアンモニウムヒドロキシド、テトラ−n−ブチルアンモニウムヒドロキシド等が挙げられる。
「含窒素複素環化合物」としては、例えば、イミダゾール、4−メチルイミダゾール、1−ベンジル−2−メチルイミダゾール、4−メチル−2−フェニルイミダゾール、ベンズイミダゾール、2−フェニルベンズイミダゾール、N−メチル2−フェニルベンズイミダゾール、N−ベンジル2−フェニルベンズイミダゾール、N−(3−ヒドロキシプロピル)2−フェニルベンズイミダゾール、等のイミダゾール類;ピリジン、2−メチルピリジン、4−メチルピリジン、2−エチルピリジン、4−エチルピリジン、2−フェニルピリジン、4−フェニルピリジン、2−メチル−4−フェニルピリジン、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、4−ヒドロキシキノリン、8−オキシキノリン、アクリジン等のピリジン類;ピペラジン、1−(2−ヒドロキシエチル)ピペラジン等のピペラジン類のほか、ピラジン、ピラゾール、ピリダジン、キノザリン、プリン、ピロリジン、ピペリジン、3−ピペリジノ−1,2−プロパンジオール、モルホリン、4−メチルモルホリン、1,4−ジメチルピペラジン、1,4−ジアザビシクロ [2.2.2] オクタン等が挙げられる。
Examples of the “quaternary ammonium hydroxide compound” include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and the like.
Examples of the “nitrogen-containing heterocyclic compound” include imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, N-methyl-2. -Imidazoles such as phenylbenzimidazole, N-benzyl 2-phenylbenzimidazole, N- (3-hydroxypropyl) 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, Pyridines such as 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine Pipette In addition to piperazines such as gin and 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, Examples include 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.
これらの含窒素有機化合物のうち、3級アミン化合物、アミド基含有化合物、含窒素複素環化合物等が好ましく、またアミド基含有化合物の中ではN−t−ブトキシカルボニル基含有アミノ化合物が好ましく、含窒素複素環化合物の中ではイミダゾール類が好ましい。これら酸拡散制御剤(F)は、単独でまたは2種以上を混合して使用できる。
酸拡散制御剤(F)の配合量は、樹脂(A)100重量部に対して、通常、5重量部以下、好ましくは3重量部以下、さらに好ましくは2重量部以下である。この場合、酸拡散制御剤の配合量が5重量部を超えると、レジストとしての感度や露光部の現像性が低下する傾向がある。なお、酸拡散制御剤の配合量が0.01重量部未満であると、プロセス条件によっては、レジストとしてのパターン形状や寸法忠実度が低下するおそれがある。
Of these nitrogen-containing organic compounds, tertiary amine compounds, amide group-containing compounds, nitrogen-containing heterocyclic compounds and the like are preferable, and among the amide group-containing compounds, Nt-butoxycarbonyl group-containing amino compounds are preferable. Among the nitrogen heterocyclic compounds, imidazoles are preferable. These acid diffusion control agents (F) can be used alone or in admixture of two or more.
The compounding amount of the acid diffusion controller (F) is usually 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the resin (A). In this case, when the compounding amount of the acid diffusion controller exceeds 5 parts by weight, the sensitivity as a resist and the developability of the exposed part tend to be lowered. If the blending amount of the acid diffusion controller is less than 0.01 parts by weight, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.
また、本発明の感放射線性樹脂組成物には、ドライエッチング耐性、パターン形状、基板との接着性等をさらに改善する作用を示す他の添加剤を配合できる。他の添加剤は酸解離性有機基を含有していても、あるいは酸解離性有機基を含有していなくてもよい。
このような他の添加剤としては、例えば、1−アダマンタンカルボン酸t−ブチル、1−アダマンタンカルボン酸t−ブトキシカルボニルメチル、1−アダマンタンカルボン酸α−ブチロラクトンエステル、1,3−アダマンタンジカルボン酸ジ−t−ブチル、1−アダマンタン酢酸t−ブチル、1−アダマンタン酢酸t−ブトキシカルボニルメチル、1,3−アダマンタンジ酢酸ジ−t−ブチル、2,5−ジメチル−2,5−ジ(アダマンチルカルボニルオキシ)ヘキサン等のアダマンタン誘導体類;デオキシコール酸t−ブチル、デオキシコール酸t−ブトキシカルボニルメチル、デオキシコール酸2−エトキシエチル、デオキシコール酸2−シクロヘキシルオキシエチル、デオキシコール酸3−オキソシクロヘキシル、デオキシコール酸テトラヒドロピラニル、デオキシコール酸メバロノラクトンエステル等のデオキシコール酸エステル類;リトコール酸t−ブチル、リトコール酸t−ブトキシカルボニルメチル、リトコール酸2−エトキシエチル、リトコール酸2−シクロヘキシルオキシエチル、リトコール酸3−オキソシクロヘキシル、リトコール酸テトラヒドロピラニル、リトコール酸メバロノラクトンエステル等のリトコール酸エステル類:アジピン酸ジメチル、アジピン酸ジエチル、アジピン酸時プロピル、アジピン酸ジn−ブチル、アジピン酸ジt−ブチル等のアルキルカルボン酸エステル類;等が挙げられる。
これらの他の添加剤は、単独でまたは2種以上を混合して使用することができる。他の添加剤の配合量は、樹脂(A)100重量部に対して、通常、50重量部以下、好ましくは30重量部以下である。この場合、添加剤の配合量が50重量部をこえると、レジストとしての耐熱性が低下する傾向がある。
In addition, the radiation-sensitive resin composition of the present invention can be blended with other additives exhibiting the action of further improving dry etching resistance, pattern shape, adhesion to the substrate, and the like. Other additives may contain an acid dissociable organic group or may not contain an acid dissociable organic group.
Examples of such other additives include 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid α-butyrolactone ester, and 1,3-adamantane dicarboxylic acid diester. -T-butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantanediacetate di-t-butyl, 2,5-dimethyl-2,5-di (adamantylcarbonyl) Adamantane derivatives such as oxy) hexane; deoxycholate t-butyl, deoxycholate t-butoxycarbonylmethyl, deoxycholate 2-ethoxyethyl, deoxycholate 2-cyclohexyloxyethyl, deoxycholate 3-oxocyclohexyl, Deoxychol Deoxycholic acid esters such as tetrahydropyranyl, deoxycholic acid mevalonolactone ester; lithocholic acid t-butyl, lithocholic acid t-butoxycarbonylmethyl, lithocholic acid 2-ethoxyethyl, lithocholic acid 2-cyclohexyloxyethyl, lithocholic acid Lithocholic acid esters such as 3-oxocyclohexyl, lithocholic acid tetrahydropyranyl, lithocholic acid mevalonolactone ester: dimethyl adipate, diethyl adipate, propyl at the time of adipic acid, di-n-butyl adipate, di-t-butyl adipate And the like, and the like.
These other additives can be used alone or in admixture of two or more. The amount of other additives is usually 50 parts by weight or less, preferably 30 parts by weight or less with respect to 100 parts by weight of the resin (A). In this case, when the compounding amount of the additive exceeds 50 parts by weight, the heat resistance as a resist tends to decrease.
また、本発明の感放射線性樹脂組成物には、塗布性、現像性等を改良する作用を示す界面活性剤を配合できる。
界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn−オクチルフェニルエーテル、ポリオキシエチレンn−ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤のほか、以下商品名で、KP341(信越化学工業(株)製)、ポリフローNo.75、同No.95(共栄社化学(株)製)、エフトップEF301、同EF303、同EF352(トーケムプロダクツ(株)製)、メガファックスF171、同F173(大日本インキ化学工業(株)製)、フロラードFC430、同FC431(住友スリーエム(株)製)、アサヒガードAG710、サーフロンS−382、同SC−101、同SC−102、同SC−103、同SC−104、同SC−105、同SC−106(旭硝子(株)製)等が挙げられる。
これらの界面活性剤は、単独でまたは2種以上を混合して使用できる。界面活性剤の配合量は、樹脂(A)100重量部に対して、通常、2重量部以下である。
In addition, the radiation-sensitive resin composition of the present invention can be blended with a surfactant exhibiting an effect of improving coatability, developability and the like.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol In addition to nonionic surfactants such as distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( Asahi Glass Co., Ltd.).
These surfactants can be used alone or in admixture of two or more. The compounding quantity of surfactant is 2 parts weight or less normally with respect to 100 weight part of resin (A).
また、本発明の感放射線性樹脂組成物には、感度等を改良する作用を示す増感剤を配合できる。好ましい増感剤としては、例えば、カルバゾール類、ベンゾフェノン類、ローズベンガル類、アントラセン類、フェノール類等が挙げられる。
これらの増感剤は、単独でまたは2種以上を混合して使用できる。増感剤の配合量は、樹脂(A)100重量部に対して、好ましくは50重量部以下である。
さらに、上記以外の添加剤としては、ハレーション防止剤、接着助剤、保存安定化剤、消泡剤等が挙げられる。
Moreover, the radiation sensitive resin composition of this invention can be mix | blended with the sensitizer which shows the effect | action which improves a sensitivity. Preferred sensitizers include, for example, carbazoles, benzophenones, rose bengals, anthracenes, phenols and the like.
These sensitizers can be used alone or in admixture of two or more. The blending amount of the sensitizer is preferably 50 parts by weight or less with respect to 100 parts by weight of the resin (A).
Furthermore, examples of additives other than those mentioned above include antihalation agents, adhesion assistants, storage stabilizers, antifoaming agents, and the like.
以下、実施例を挙げて、本発明の実施の形態をさらに具体的に説明する。ここで、部は、特記しない限り重量基準である。
合成例、実施例および比較例における各測定・評価は、下記の要領で行なった。
(1)MwおよびMn
東ソー(株)製GPCカラム(G2000HXL 2本、G3000HXL 1本、G4000HXL 1本)を用い、流量1.0ミリリットル/分、溶出溶媒テトラヒドロフラン、カラム温度40℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィー(GPC)により測定した。
(2)kD値
合成例3〜6で得られる樹脂(A−3)〜(A−6)に関して、規定濃度の樹脂溶液を調製後充分にローター攪拌を行ない均一溶液を得た。このとき用いた溶剤(B)の混合比は、プロピレングリコールモノメチルエーテルアセテート/シクロヘキサノン/γ−ブチロラクトン=53.46/43.85/2.69(重量%)を用いた。この樹脂溶液を上記混合比の溶剤(B)を用いて規定濃度に希釈したサンプルを孔径0.2ミクロンのフィルター(有機溶媒用)で濾過し、メタノール還流洗浄器にて2時間以上洗浄を行なった直径20mmの石英ガラスセルに注入した。溶液粘度は温度に依存するため、23.00±0.02℃で精密に制御して動的光散乱測定を行なった。各散乱角度における拡散係数の平均値を、その濃度における見かけ上の拡散係数Dとする。このDを濃度c(単位重量%)に対してプロットした図において切片はD0、勾配はD0×kDを表すので、両者よりそれぞれの樹脂溶液のkD値を得ることができる。
(3)放射線透過率
組成物溶液を石英ガラス上に塗布し、表2に示した温度条件に保持したホットプレート上で表2に示した条件の間PBを行って形成した膜厚0.34μmのレジスト被膜について、波長193nmにおける吸光度から、放射線透過率を算出して、遠紫外線領域における透明性の尺度とした。
(4)感度
ArF光源にて露光を行なう場合、ウエハー表面に膜厚77nmのARC29A((Brewer Science社製)膜を形成したシリコーンウエハー(ARC29A))を用い、各組成物溶液を、基板上にスピンコートにより塗布し、ホットプレート上にて、表2に示す条件でPBを行なって形成した膜厚215nmのレジスト被膜に、ニコン製ArFエキシマレーザー露光装置(S306C 開口数0.78)を用い、マスクパターンを介して露光した。その後、表2に示す条件でPEBを行なったのち、2.38重量%のテトラメチルアンモニウムヒドロキシド水溶液により、25℃で40秒間現像し、水洗し、乾燥して、ポジ型のレジストパターンを形成した。このとき、マスクにおいて線幅100nmでピッチ1100nm(1L10S)が線幅70nmになるような露光量(マスクバイアス:+30nm)を最適露光量とし、この最適露光量を感度とした。
(5)バイアス
上記最適露光量におけるマスクにおいて線幅100nmでピッチ220nm(1L1.2S)の線幅と上記70nmとの差をバイアスとする。
Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. Here, the part is based on weight unless otherwise specified.
Measurements and evaluations in the synthesis examples, examples, and comparative examples were performed in the following manner.
(1) Mw and Mn
Using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, monodisperse polystyrene was used as the standard under the analysis conditions of a flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. Measured by gel permeation chromatography (GPC).
(2) k D value With respect to the resins (A-3) to (A-6) obtained in Synthesis Examples 3 to 6, a rotor solution was sufficiently stirred after preparing a resin solution having a specified concentration to obtain a uniform solution. As a mixing ratio of the solvent (B) used at this time, propylene glycol monomethyl ether acetate / cyclohexanone / γ-butyrolactone = 53.46 / 43.85 / 2.69 (% by weight) was used. A sample obtained by diluting the resin solution to a specified concentration with the solvent (B) having the above mixing ratio is filtered through a filter (for organic solvent) having a pore diameter of 0.2 microns and washed with a methanol reflux washer for 2 hours or more. It was poured into a quartz glass cell having a diameter of 20 mm. Since the solution viscosity depends on the temperature, dynamic light scattering measurement was performed with precise control at 23.00 ± 0.02 ° C. The average value of the diffusion coefficient at each scattering angle is defined as an apparent diffusion coefficient D at that concentration. In the graph in which D is plotted against the concentration c (unit weight%), the intercept represents D 0 and the gradient represents D 0 × k D , so that the k D value of each resin solution can be obtained from both.
(3) Radiation transmittance A film thickness of 0.34 μm formed by applying the composition solution on quartz glass and performing PB on the hot plate kept at the temperature condition shown in Table 2 during the conditions shown in Table 2. With respect to the resist film, the radiation transmittance was calculated from the absorbance at a wavelength of 193 nm and used as a measure of transparency in the far ultraviolet region.
(4) Sensitivity When performing exposure using an ArF light source, a 77 nm-thick ARC29A film (made by Brewer Science) (silicon wafer (ARC29A)) is used on the wafer surface, and each composition solution is applied onto the substrate. Using a Nikon ArF excimer laser exposure apparatus (S306C numerical aperture 0.78) on a resist film having a film thickness of 215 nm formed by spin coating and performing PB on a hot plate under the conditions shown in Table 2. Exposure was through a mask pattern. Thereafter, PEB is performed under the conditions shown in Table 2, and then developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 40 seconds, washed with water, and dried to form a positive resist pattern. did. At this time, the exposure amount (mask bias: +30 nm) at which the line width is 100 nm and the pitch is 1100 nm (1L10S) is 70 nm in the mask is set as the optimal exposure amount, and this optimal exposure amount is set as the sensitivity.
(5) Bias The difference between the line width of 100 nm and the pitch of 220 nm (1L1.2S) in the mask at the above optimum exposure amount and the above 70 nm is defined as the bias.
(6)現像欠陥
現像欠陥はケー・エル・エー・テンコール(株)社製の欠陥検査装置(KLA2351)を用いる方法により評価した。欠陥検査用ウエハーは、次のように作製した。ARC29A(日産化学社製)77nmをウエハー基板に作成した基板上に、評価用レジストを210nmの膜厚で塗布後126℃/90秒の条件でPBし、Nikon社製ArF露光装置(S306C)により180nmのアクティブパターンが全面にあるマスクを介してその最適露光量にて露光した。露光後、126℃/90秒の条件でPEBを行なった後、2.38重量%のテトラメチルアンモニウムヒドロキシド水溶液により23℃で40秒間現像し、水洗、乾燥して、欠陥検査用ウエハーを作製した。上記の塗布、焼成および現像は東京エレクトロン社製のACT8を使用し、すべてインラインで実施した。
上述の方法により作成した欠陥検査用ウエハーを、ケー・エル・エー・テンコール(株)社製の欠陥検査装置(KLA2351)を使用することにより露光部の現像欠陥を検査した。欠陥総数の検査は、アレイモードで観察して、比較イメージとピクセル単位の重ね合わせによって生じる差異から抽出される欠陥総数を検出することにより行なった。欠陥総数の検出は、0.15μm以上の欠陥を検出できるように、この装置の感度を設定して行なった。
(7)LER
上記最適露光量で形成された70nmのラインパターンにおいて、日立ハイテクノロジーズ社製S9220を用いて、その線幅を別のY軸上で10点以上線幅を測定したときの線幅ばらつき(3σ)を計測した。そのばらつき(3σ)が15nm以上の場合「不良」とし、15nm未満の場合「良好」とした。
(6) Development defect The development defect was evaluated by a method using a defect inspection apparatus (KLA2351) manufactured by KLA-Tencor Corporation. The wafer for defect inspection was produced as follows. An ARC29A (manufactured by Nissan Chemical Industries, Ltd.) 77 nm on a wafer substrate was coated with a resist for evaluation with a film thickness of 210 nm and then subjected to PB under conditions of 126 ° C./90 seconds, and then Nikon ArF exposure apparatus (S306C). The exposure was performed at the optimum exposure amount through a mask having an active pattern of 180 nm on the entire surface. After exposure, PEB was performed at 126 ° C./90 seconds, developed with 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 40 seconds, washed with water and dried to produce a wafer for defect inspection. did. The above coating, baking and development were all performed inline using ACT8 manufactured by Tokyo Electron.
The defect inspection wafer produced by the above-described method was inspected for development defects in the exposed portion by using a defect inspection apparatus (KLA2351) manufactured by KLA-Tencor Corporation. The inspection of the total number of defects was performed by observing in the array mode and detecting the total number of defects extracted from the difference caused by the comparison image and the pixel unit. The total number of defects was detected by setting the sensitivity of this apparatus so that defects of 0.15 μm or more could be detected.
(7) LER
Line width variation (3σ) when the line width is measured at 10 points or more on another Y-axis using S9220 manufactured by Hitachi High-Technologies Corporation in the 70 nm line pattern formed at the optimum exposure amount. Was measured. When the variation (3σ) was 15 nm or more, it was judged as “bad”, and when it was less than 15 nm, it was judged as “good”.
合成例1
合成例2
合成例3
合成例4
合成例5
合成例6
下記表1に、樹脂(A−3)〜(A−6)について測定された係数(kD)を示す。
実施例1
樹脂(A−1)、樹脂(A−2)および樹脂(A−3)を表1に示す割合で混合した混合物を表2に示す他の成分を配合した感放射線性樹脂組成物溶液について、表3の条件で評価し、評価結果を表4に示す。なお、樹脂(A−1)および樹脂(A−2)の係数(kD)はそれぞれ−2.4g/gおよび−2.9g/gであった。
表2における重合体(A−1)〜(A−6)以外の成分は以下の通りである。
レジスト溶剤(B)
B−1:プロピレングリコールモノメチルエーテルアセテート
B−2:シクロヘキサノン
B−3:γ−ブチロラクトン
酸発生剤(C)
C−1: 1−(4−n−ブトキシナフタレンー1−イル)テトラヒドロチオフェニウム パーフルオロ−n−オクタンスルホネート
酸拡散制御剤(F)
D−1:N−t−ブトキシカルボニル−2−フェニルベンズイミダゾール
添加剤(E)
E−1:デオキシコール酸t−ブトキシカルボニルメチル
Example 1
About the radiation sensitive resin composition solution which mix | blended the other component which shows the mixture which mixed resin (A-1), resin (A-2), and resin (A-3) in the ratio shown in Table 1 in Table 2, Evaluation was performed under the conditions shown in Table 3, and the evaluation results are shown in Table 4. The coefficients (k D ) of Resin (A-1) and Resin (A-2) were −2.4 g / g and −2.9 g / g, respectively.
Components other than the polymers (A-1) to (A-6) in Table 2 are as follows.
Resist solvent (B)
B-1: Propylene glycol monomethyl ether acetate B-2: Cyclohexanone B-3: γ-Butyrolactone Acid generator (C)
C-1: 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate Acid diffusion controller (F)
D-1: Nt-butoxycarbonyl-2-phenylbenzimidazole additive (E)
E-1: Deoxycholic acid t-butoxycarbonylmethyl
実施例2
樹脂(A−3)を樹脂(A−4)に代える以外は実施例1と同様にして係数(kD)の測定、および感放射線性樹脂組成物溶液を作製して、表3の条件で評価し、評価結果を表4に示す。
Example 2
Except that the resin (A-3) is replaced with the resin (A-4), the measurement of the coefficient (k D ) and the radiation-sensitive resin composition solution are made in the same manner as in Example 1, and the conditions in Table 3 are used. The evaluation results are shown in Table 4.
実施例3
樹脂(A−3)を樹脂(A−5)に代える以外は実施例1と同様にして係数(kD)の測定、および感放射線性樹脂組成物溶液を作製して、表3の条件で評価し、評価結果を表4に示す。
Example 3
The coefficient (k D ) was measured in the same manner as in Example 1 except that the resin (A-3) was replaced with the resin (A-5), and a radiation-sensitive resin composition solution was prepared. The evaluation results are shown in Table 4.
実施例4
樹脂(A−3)を樹脂(A−6)に代える以外は実施例1と同様にして係数(kD)の測定、および感放射線性樹脂組成物溶液を作製して、表3の条件で評価し、評価結果を表4に示す。
Except that the resin (A-3) is replaced with the resin (A-6), the measurement of the coefficient (k D ) and the radiation-sensitive resin composition solution are made in the same manner as in Example 1, and the conditions in Table 3 are used. The evaluation results are shown in Table 4.
表4に示すように、感放射線性樹脂の係数(kD)値により、現像欠陥やLERの性能を予測できる。すなわち、複数配合される少なくとも1つの樹脂のkD値が−2.20g/g以上あれば現像欠陥やLER特性に優れた感放射線性樹脂組成物が得られる。 As shown in Table 4, development defect and LER performance can be predicted from the coefficient (k D ) value of the radiation sensitive resin. That is, if the k D value of at least one resin to be blended is −2.20 g / g or more, a radiation-sensitive resin composition excellent in development defects and LER characteristics can be obtained.
感放射線性樹脂の現像特性が係数(kD)により評価・選別できるので、より高い集積度が求められ半導体分野に適用できる。
また、この評価方法を用いることで、KrFエキシマレーザーあるいはArFエキシマレーザー等の遠紫外線、シンクロトロン放射線等のX線、電子線等の荷電粒子線の如き各種の放射線を使用する微細加工に有用な化学増幅型レジストとして好適に使用できる感放射線性樹脂組成物の製造に適用できる。
Since the development characteristics of the radiation-sensitive resin can be evaluated and selected by the coefficient (k D ), a higher degree of integration is required and can be applied to the semiconductor field.
Moreover, by using this evaluation method, it is useful for microfabrication using various types of radiation such as deep ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. The present invention can be applied to the production of a radiation sensitive resin composition that can be suitably used as a chemically amplified resist.
Claims (2)
前記酸解離性基含有樹脂(A)の少なくとも1種は、該樹脂(A)のレジスト溶剤(B)溶液の動的光散乱測定により、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数(kD)が−2.20g/g以上であることを特徴とする感放射線性樹脂組成物。 An acid-dissociable group-containing resin (A) that is insoluble or hardly soluble in alkali and easily soluble in alkali by the action of an acid, alone or in combination, a resist solvent (B), and a radiation-sensitive acid generator (C And a radiation sensitive resin composition comprising:
At least one of the acid dissociable group-containing resin (A) is contained in a solution of a radiation sensitive resin accompanying a change in the concentration of the solution by dynamic light scattering measurement of a resist solvent (B) solution of the resin (A). A radiation-sensitive resin composition having a coefficient (k D ) representing a change in diffusion coefficient of -2.20 g / g or more.
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