JP2018096817A - Method of evaluating protective performance of polymer - Google Patents
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- 229920000642 polymer Polymers 0.000 title claims abstract description 150
- 230000001681 protective effect Effects 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007654 immersion Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000011156 evaluation Methods 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052710 silicon Inorganic materials 0.000 abstract description 33
- 239000010703 silicon Substances 0.000 abstract description 33
- 238000011109 contamination Methods 0.000 description 17
- 238000005530 etching Methods 0.000 description 15
- 230000003746 surface roughness Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Description
本発明は、シリコンウェーハ表面を保護するためのポリマーの保護性評価方法に関する。 The present invention relates to a polymer protective property evaluation method for protecting a silicon wafer surface.
半導体シリコンウェーハの加工は複数の工程を必要とするため、それに伴い工程間の搬送時あるいは保管時のウェーハ変化に注意が必要である。特に、ベアシリコンを浸水状態で次工程に搬送する場合、ベアシリコンは純水からアルカリのｐＨ領域（ｐＨ７以上）で容易に面荒れが発生し、また、Ｃｕなどの酸化力の高い金属により表面が局所的に反応し、ピット化してしまうことが知られている。 Since processing of a semiconductor silicon wafer requires a plurality of processes, it is necessary to pay attention to changes in the wafer during transport or storage between the processes. In particular, when bare silicon is transported to the next process in a submerged state, bare silicon is easily roughened from pure water to an alkaline pH region (pH 7 or higher), and the surface is made of a metal having high oxidizing power such as Cu. Is known to react locally and form pits.
これらの現象を抑制するための方策として、ベアシリコンの表面に自然酸化膜を形成する、もしくはベアシリコンの上にポリマーを吸着させる（特許文献１）等の手段でベアシリコンを保護する方策があるが、前者はオゾンなどの特別な薬液と排水設備を必要とするためコストの観点で難がある。後者はより簡便な方法でベアシリコンの表面保護を実現できるが、自然酸化膜に比べて知見が少なく、例えばどのようなポリマーでどのような吸着方法を用いると保護性が高まるか等の評価技術が確立されていない。 As a measure for suppressing these phenomena, there is a measure to protect bare silicon by means such as forming a natural oxide film on the surface of bare silicon or adsorbing a polymer on bare silicon (Patent Document 1). However, since the former requires special chemicals such as ozone and drainage facilities, it is difficult in terms of cost. The latter can realize surface protection of bare silicon by a simpler method, but has less knowledge than natural oxide film, for example, evaluation technology such as what kind of polymer and what kind of adsorption method improves protection Is not established.
シリコンウェーハ表面を保護するためのポリマーの保護性を評価する方法としては、例えば、ＴＥＭ（透過型電子顕微鏡）等によりポリマーが吸着したウェーハを分析し、ポリマー吸着層の厚さを評価する方法が考えられるが、ポリマーは電子線により容易に壊れてしまうため、このような方法では評価は困難である。また、別の方法として、Ｃｕなどの金属により表面にポリマーが吸着したウェーハを故意に汚染させ、その後パーティクルカウンターにて発生したピットの数を数える方法もあるが、浸漬槽、その後の洗浄槽を金属により汚染してしまい、その後の実験に影響が出るため、この方法も好ましい方法とは言えない。このように、ポリマーの保護性を安価かつ簡便に評価することは難しく、ポリマーの保護性を安価かつ簡便に評価できる方法の開発が求められていた。 As a method for evaluating the protection property of the polymer for protecting the silicon wafer surface, for example, there is a method of analyzing the wafer on which the polymer is adsorbed by TEM (transmission electron microscope) and evaluating the thickness of the polymer adsorbing layer. Although it is conceivable, since the polymer is easily broken by the electron beam, evaluation by such a method is difficult. As another method, there is a method of intentionally contaminating a wafer having a polymer adsorbed on the surface with a metal such as Cu, and then counting the number of pits generated by a particle counter. This method is not preferable because it is contaminated with metal and affects subsequent experiments. Thus, it is difficult to evaluate the protective properties of the polymer at low cost and simply, and development of a method capable of evaluating the protective properties of the polymer at low cost and in a simple manner has been demanded.
本発明は、上記問題を解決するためになされたものであり、シリコンウェーハ表面を保護するためのポリマーの保護性を安価かつ簡便に評価することが可能な評価方法を提供することを目的とする。 The present invention has been made to solve the above-described problem, and an object of the present invention is to provide an evaluation method capable of inexpensively and simply evaluating the protective properties of a polymer for protecting the silicon wafer surface. .
上記課題を達成するために、本発明では、ウェーハ表面に吸着することでウェーハ表面を保護するポリマーの保護性を評価する方法であって、純水又は純水に任意のアルカリを溶解させたｐＨ７以上の溶液に、前記ポリマーにより表面が保護されたウェーハの一部又は全部を浸漬させ、該浸漬後のウェーハのＨａｚｅと浸漬前のウェーハのＨａｚｅとの差、又は前記浸漬後のウェーハの浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差に基づいて前記ポリマーの保護性を評価するポリマーの保護性評価方法を提供する。 In order to achieve the above object, the present invention is a method for evaluating the protective property of a polymer that protects a wafer surface by adsorbing to the wafer surface, and has a pH of 7 in which any alkali is dissolved in pure water or pure water. A part or all of the wafer whose surface is protected by the polymer is immersed in the above solution, and the difference between the haze of the wafer after the immersion and the haze of the wafer before the immersion, or the immersion part of the wafer after the immersion There is provided a method for evaluating the protective property of a polymer, wherein the protective property of the polymer is evaluated based on the difference between the haze of the polymer and the haze of the non-immersed part.
このようなポリマーの保護性評価方法であれば、ポリマーにより表面が保護されたウェーハを純水又はｐＨ７以上の溶液に浸漬させてエッチングを行った際の、エッチング前後のＨａｚｅの差、あるいはエッチングされた箇所とエッチングされていない箇所のＨａｚｅの差に基づいて、ポリマーの保護性を安価かつ簡便に評価することができる。 With such a method for evaluating the protective property of a polymer, the difference in Haze before and after etching when a wafer whose surface is protected by a polymer is immersed in pure water or a solution of pH 7 or higher, or etching is performed. The protective properties of the polymer can be evaluated inexpensively and easily based on the difference in haze between the spot and the part not etched.
また、前記浸漬前のウェーハのＨａｚｅを、前記ポリマーにより表面を保護する前のウェーハのＨａｚｅとすることが好ましい。 Moreover, it is preferable that the haze of the wafer before the immersion is the haze of the wafer before the surface is protected by the polymer.
このようにすることで、浸漬前のウェーハのＨａｚｅをより正確に測定することができ、結果として、ポリマーの保護性をより正確に評価することができる。 By doing in this way, the haze of the wafer before immersion can be measured more accurately, and as a result, the protective properties of the polymer can be more accurately evaluated.
また、本発明のポリマーの保護性評価方法では、前記ポリマーにより表面が保護されたウェーハとして、前記ポリマーを溶解させた溶液にＨＦ洗浄により表面酸化膜を除去したウェーハを浸漬させることで表面に前記ポリマーを吸着させたウェーハ、又は前記ポリマーを溶解させた溶液を染み込ませた布製の素材と前記ＨＦ洗浄により表面酸化膜を除去したウェーハを接触させることで表面に前記ポリマーを吸着させたウェーハを用いることができる。 Further, in the polymer protective evaluation method of the present invention, as the wafer whose surface is protected by the polymer, the wafer from which the surface oxide film has been removed by HF cleaning is immersed in a solution in which the polymer is dissolved, and the wafer is immersed in the surface. A wafer having a polymer adsorbed on the surface thereof is used by contacting a wafer on which a polymer is adsorbed or a cloth material soaked with a solution in which the polymer is dissolved with a wafer from which a surface oxide film has been removed by HF cleaning. be able to.
本発明のポリマーの保護性評価方法では、例えばこのような方法で表面にポリマーを吸着させたウェーハを用いてポリマーの保護性を評価することができる。 In the polymer protective property evaluation method of the present invention, for example, the protective property of the polymer can be evaluated using a wafer having the polymer adsorbed on the surface by such a method.
以上のように、本発明のポリマーの保護性評価方法であれば、ポリマーにより表面が保護されたウェーハを純水又はｐＨ７以上の溶液に浸漬させてエッチングを行った際の、エッチング前後のＨａｚｅの差、あるいはエッチングされた箇所とエッチングされていない箇所のＨａｚｅの差に基づいて、ポリマーの保護性を安価で簡便かつ正確に評価することができる。また、複数種類のポリマーを用いて評価を行えば、ポリマーの保護性を複数のポリマー間で相対的に評価することもできる。 As described above, in the polymer protective evaluation method of the present invention, the Haze before and after etching when etching is performed by immersing a wafer whose surface is protected by the polymer in pure water or a solution of pH 7 or higher. Based on the difference or the difference in Haze between the etched part and the non-etched part, the protective property of the polymer can be evaluated inexpensively, simply and accurately. Moreover, if evaluation is performed using a plurality of types of polymers, the protective properties of the polymers can be relatively evaluated among the plurality of polymers.
上述のように、ＴＥＭ等によりポリマー吸着層の厚さを評価する方法やＣｕ故意汚染により発生したピットの数を数える方法では、ポリマーの保護性を安価かつ簡便に評価することは難しく、ポリマーの保護性を安価かつ簡便に評価できる方法の開発が求められていた。 As described above, the method for evaluating the thickness of the polymer adsorbing layer by TEM or the like and the method for counting the number of pits generated by Cu intentional contamination make it difficult to evaluate the protective properties of the polymer at low cost and easily. Development of a method that can easily and inexpensively evaluate the protective property has been demanded.
そこで、本発明者らは、ポリマーを吸着したウェーハの粗さ変化に着目した。一般的に面方位（１００）のシリコンは、ＨＦ処理等により水素終端していると、ｐＨ７以上の中性から塩基性条件下で荒れることが分かっている。この現象は（１００）方向と（１１１）方向のエッチングレート差に起因する。 Therefore, the present inventors paid attention to the change in roughness of the wafer that adsorbed the polymer. In general, it is known that silicon having a plane orientation (100) is roughened under neutral to basic conditions at pH 7 or higher when hydrogen-terminated by HF treatment or the like. This phenomenon is caused by a difference in etching rate between the (100) direction and the (111) direction.
図３に示されるように、表面酸化膜のないベアシリコン１をポリマー保護することなく、一部分のみを残して（即ち、浸漬部１ａと非浸漬部１ｂが生じるように）純水２中に浸漬させ、その後ＫＬＡテンコール社製のパーティクルカウンターＳＰ２を用いてＨａｚｅを測定すると、図４に示されるように浸漬部１ａは白く、非浸漬部１ｂは黒くなり、浸漬部１ａと非浸漬部１ｂで明瞭なコントラストが発生する。ここで、白色に見える部分はＨａｚｅ悪化部分である。これは、浸漬部でエッチングが進み表面荒れが促進された結果である。一方、本発明者らが検討したところ、ベアシリコンの表面にポリマーが吸着している状態では、ｐＨ７以上の中性から塩基性条件下においても表面が荒れにくくなるため、Ｈａｚｅは悪化しにくくなることが分かった。更に、本発明者らが検討したところ、ポリマーの金属汚染耐性はエッチングによる面荒れ耐性と強く相関していることが分かった。 As shown in FIG. 3, the bare silicon 1 having no surface oxide film is immersed in pure water 2 without polymer protection, leaving only a part (that is, so that the immersion part 1a and the non-immersion part 1b are generated). Then, when the haze is measured using a particle counter SP2 manufactured by KLA Tencor, the immersion part 1a is white and the non-immersion part 1b is black as shown in FIG. 4, and the immersion part 1a and the non-immersion part 1b are clear. Contrast occurs. Here, the portion that appears white is a haze-deteriorating portion. This is a result of the progress of etching and the surface roughness being promoted in the immersion part. On the other hand, when the present inventors examined, in the state which the polymer adsorb | sucked to the surface of bare silicon, since the surface becomes difficult to be rough under neutral to basic conditions of pH 7 or more, Haze is not easily deteriorated. I understood that. Furthermore, as a result of studies by the present inventors, it has been found that the metal contamination resistance of the polymer is strongly correlated with the surface roughness resistance due to etching.
これらのことから、本発明者らは、ポリマーにより表面が保護されたウェーハを純水又はｐＨ７以上の溶液に浸漬させてエッチングを行った際の、エッチング前後のＨａｚｅの差、あるいはエッチングされた箇所とエッチングされていない箇所のＨａｚｅの差（以下、「ΔＨａｚｅ」とも称する）を金属汚染耐性及びエッチングによる面荒れ耐性（即ち、ポリマーの保護性）の指標とみなし、このΔＨａｚｅの多寡を評価することでポリマーの保護性を安価かつ簡便に評価できることを見出し、本発明を完成させた。 From these facts, the present inventors found that the difference in Haze before and after etching or the etched portion when the wafer whose surface was protected by the polymer was immersed in pure water or a solution of pH 7 or higher was etched. The difference between the haze and the unetched portion (hereinafter also referred to as “ΔHaze”) is regarded as an index of metal contamination resistance and surface roughness resistance due to etching (that is, polymer protection), and the amount of ΔHaze is evaluated. Thus, the inventors have found that the protective properties of the polymer can be evaluated inexpensively and simply, and completed the present invention.
即ち、本発明は、ウェーハ表面に吸着することでウェーハ表面を保護するポリマーの保護性を評価する方法であって、純水又は純水に任意のアルカリを溶解させたｐＨ７以上の溶液に、前記ポリマーにより表面が保護されたウェーハの一部又は全部を浸漬させ、該浸漬後のウェーハのＨａｚｅと浸漬前のウェーハのＨａｚｅとの差、又は前記浸漬後のウェーハの浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差に基づいて前記ポリマーの保護性を評価するポリマーの保護性評価方法である。 That is, the present invention is a method for evaluating the protective properties of a polymer that protects a wafer surface by adsorbing to the wafer surface, and the pure water or a solution having a pH of 7 or more in which arbitrary alkali is dissolved in pure water, A part or all of the wafer whose surface is protected by the polymer is immersed, and the difference between the Haze of the wafer after the immersion and the Haze of the wafer before the immersion, or the Haze and the non-immersion part of the immersion part of the wafer after the immersion This is a polymer protective evaluation method for evaluating the protective properties of the polymer based on the difference from Haze.
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
図１に本発明のポリマーの保護性評価方法の一例のフロー図を示す。図１の方法では、まず、ウェーハを用意し（図１の（Ａ１）工程）、ポリマーをウェーハ表面に吸着させて、ポリマーによりウェーハ表面を保護する（図１の（Ａ２）工程）。次に、ポリマーにより表面が保護されたウェーハの一部を（浸漬部と非浸漬部が生じるように）純水に浸漬させる（図１の（Ａ３）工程）。次に、浸漬後のウェーハの浸漬部のＨａｚｅと非浸漬部のＨａｚｅを測定し（図１の（Ａ４）工程）、浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差（ΔＨａｚｅ）を求める（図１の（Ａ５）工程）。そして、求めたΔＨａｚｅに基づいてポリマーの保護性を評価する（図１の（Ａ６））。 FIG. 1 shows a flow chart of an example of the method for evaluating the protective properties of the polymer of the present invention. In the method of FIG. 1, first, a wafer is prepared (step (A1) in FIG. 1), the polymer is adsorbed on the wafer surface, and the wafer surface is protected by the polymer (step (A2) in FIG. 1). Next, a part of the wafer whose surface is protected by the polymer is immersed in pure water (so that an immersion part and a non-immersion part are generated) (step (A3) in FIG. 1). Next, the haze of the immersed part of the wafer after immersion and the haze of the non-immersed part are measured (step (A4) in FIG. 1), and the difference (ΔHaze) between the haze of the immersed part and the haze of the non-immersed part is obtained ( Step (A5) in FIG. Then, the protective properties of the polymer are evaluated based on the obtained ΔHaze ((A6) in FIG. 1).
本発明のポリマーの保護性評価方法では、このように浸漬後のウェーハの浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差（ΔＨａｚｅ）に基づいて、ポリマーの保護性を評価することができる。この場合、ポリマーの保護性が高ければ、ウェーハの浸漬部におけるエッチングによる面荒れが抑制され、浸漬部のＨａｚｅが小さくなるため、ΔＨａｚｅが小さくなる。一方、ポリマーの保護性が低ければ、浸漬部におけるエッチングによる面荒れが抑制されず、浸漬部のＨａｚｅが大きくなるため、ΔＨａｚｅが大きくなる。このことから、ΔＨａｚｅが小さければ小さいほど、ポリマーの保護性が高いと評価することができる。 In the polymer protective property evaluation method of the present invention, the protective property of the polymer can be evaluated based on the difference (ΔHaze) between the haze of the immersed portion and the non-immersed portion of the wafer after immersion. In this case, if the protection property of the polymer is high, surface roughness due to etching in the immersion part of the wafer is suppressed, and the haze of the immersion part is reduced, so that ΔHaze is reduced. On the other hand, if the protection property of the polymer is low, surface roughness due to etching in the immersion part is not suppressed, and the haze of the immersion part increases, so ΔHaze increases. From this, it can be evaluated that the smaller the ΔHaze, the higher the protection of the polymer.
また、図２に本発明のポリマーの保護性評価方法の別の一例のフロー図を示す。図２の方法では、まず、ウェーハを用意し（図２の（Ｂ１）工程）、ポリマーにより表面を保護する前のウェーハのＨａｚｅ（即ち、浸漬前のウェーハのＨａｚｅ）を測定する（図２の（Ｂ２）工程）。次に、ポリマーをウェーハ表面に吸着させて、ポリマーによりウェーハ表面を保護する（図２の（Ｂ３）工程）。次に、ポリマーにより表面が保護されたウェーハの全部を純水に浸漬させる（図２の（Ｂ４）工程）。次に、浸漬後のウェーハのＨａｚｅを測定し（図２の（Ｂ５）工程）、浸漬後のＨａｚｅと浸漬前のＨａｚｅとの差（ΔＨａｚｅ）を求める（図２の（Ｂ６）工程）。そして、求めたΔＨａｚｅに基づいてポリマーの保護性を評価する（図２の（Ｂ７））。 FIG. 2 shows a flow chart of another example of the polymer protective evaluation method of the present invention. In the method of FIG. 2, first, a wafer is prepared (step (B1) in FIG. 2), and the haze of the wafer before the surface is protected by the polymer (that is, the haze of the wafer before immersion) is measured (FIG. 2). (B2) Step). Next, the polymer is adsorbed on the wafer surface, and the wafer surface is protected by the polymer (step (B3) in FIG. 2). Next, the entire wafer whose surface is protected by the polymer is immersed in pure water (step (B4) in FIG. 2). Next, the haze of the wafer after immersion is measured (step (B5) in FIG. 2), and the difference (ΔHaze) between the haze after immersion and the haze before immersion is obtained (step (B6) in FIG. 2). Then, the protective properties of the polymer are evaluated based on the obtained ΔHaze ((B7) in FIG. 2).
本発明のポリマーの保護性評価方法では、このように浸漬後のウェーハのＨａｚｅと浸漬前のウェーハのＨａｚｅとの差（ΔＨａｚｅ）に基づいて、ポリマーの保護性を評価することもできる。この場合、ポリマーの保護性が高ければ、ウェーハを浸漬した際のエッチングによる面荒れが抑制され、浸漬後のウェーハのＨａｚｅが小さくなるため、ΔＨａｚｅが小さくなる。一方、ポリマーの保護性が低ければ、ウェーハを浸漬した際のエッチングによる面荒れが抑制されず、浸漬後のウェーハのＨａｚｅが大きくなるため、ΔＨａｚｅが大きくなる。このことから、ΔＨａｚｅが小さければ小さいほど、ポリマーの保護性が高いと評価することができる。 In the polymer protective property evaluation method of the present invention, the protective property of the polymer can also be evaluated based on the difference (ΔHaze) between the haze of the wafer after immersion and the haze of the wafer before immersion. In this case, if the protective property of the polymer is high, surface roughness due to etching when the wafer is immersed is suppressed, and the haze of the wafer after immersion is reduced, so that ΔHaze is reduced. On the other hand, if the protective property of the polymer is low, surface roughness due to etching when the wafer is immersed is not suppressed, and the haze of the wafer after immersion increases, so ΔHaze increases. From this, it can be evaluated that the smaller the ΔHaze, the higher the protection of the polymer.
なお、図２のフローのように、浸漬前のウェーハのＨａｚｅを、ポリマーにより表面を保護する前のウェーハのＨａｚｅとすることで、浸漬前のウェーハのＨａｚｅをより正確に測定することができ、結果として、ポリマーの保護性をより正確に評価することができるため、好ましい。 As shown in the flow of FIG. 2, by setting the Haze of the wafer before immersion to the Haze of the wafer before protecting the surface with the polymer, the Haze of the wafer before immersion can be measured more accurately. As a result, the protective properties of the polymer can be more accurately evaluated, which is preferable.
本発明のポリマーの保護性評価方法において、純水又は純水に任意のアルカリを溶解させたｐＨ７以上の溶液に、ポリマーにより表面が保護されたウェーハを浸漬させる際には、特に限定されないが、１２〜４８時間程度浸漬させることが好ましく、例えば、２４時間程度浸漬させることが好ましい。また、光による面荒れを抑制するために、浸漬は暗所で行うことが好ましい。 In the polymer protective property evaluation method of the present invention, when the wafer whose surface is protected by the polymer is immersed in pure water or a solution of pH 7 or higher in which an arbitrary alkali is dissolved in pure water, it is not particularly limited. It is preferable to immerse for about 12 to 48 hours, for example, it is preferable to immerse for about 24 hours. Moreover, in order to suppress the surface roughness by light, it is preferable to perform immersion in a dark place.
本発明のポリマーの保護性評価方法において、Ｈａｚｅの測定は、特に限定されないが、例えば、ＫＬＡテンコール社製のパーティクルカウンターＳＰ２などを用いて行うことができる。 In the polymer protective property evaluation method of the present invention, the measurement of Haze is not particularly limited, but can be performed using, for example, a particle counter SP2 manufactured by KLA Tencor.
また、本発明のポリマーの保護性評価方法において、浸漬後のウェーハのＨａｚｅ測定の前には、過酸化水素を含む洗浄液（例えば、ＳＣ１など）を用いてウェーハを洗浄し、ウェーハに付着しているポリマーを除去することが好ましい。 In the polymer protective property evaluation method of the present invention, before the haze measurement of the wafer after immersion, the wafer is washed with a cleaning solution containing hydrogen peroxide (for example, SC1) and adhered to the wafer. It is preferable to remove the polymer.
また、本発明のポリマーの保護性評価方法において、ポリマーをウェーハ表面に吸着させる方法は、特に限定されないが、例えば、ポリマーを溶解させた溶液にＨＦ洗浄により表面酸化膜を除去したウェーハを浸漬させることで表面にポリマーを吸着させる方法や、ポリマーを溶解させた溶液を染み込ませた軟質の布製の素材とＨＦ洗浄により表面酸化膜を除去したウェーハを擦り合わせる等して接触させることで表面にポリマーを吸着させる方法などを挙げることができる。 In the polymer protective property evaluation method of the present invention, the method for adsorbing the polymer to the wafer surface is not particularly limited. For example, the wafer from which the surface oxide film is removed by HF cleaning is immersed in a solution in which the polymer is dissolved. By adsorbing the polymer to the surface, or by bringing the soft cloth material soaked with the solution in which the polymer is dissolved into the wafer with the surface oxide film removed by HF cleaning, the polymer is brought into contact with the surface. And the like.
以上説明したような本発明のポリマーの保護性評価方法であれば、ポリマーにより表面が保護されたウェーハを純水又はｐＨ７以上の溶液に浸漬させてエッチングを行った際の、エッチング前後のＨａｚｅの差、あるいはエッチングされた箇所とエッチングされていない箇所のＨａｚｅの差に基づいて、ポリマーの保護性を安価で簡便かつ正確に評価することができる。また、複数の種類のポリマーを用いて評価を行えば、ポリマーの保護性を複数のポリマー間で相対的に評価することもできる。 If it is the protection evaluation method of the polymer of this invention which was demonstrated above, the wafer of which the surface was protected by the polymer was etched by immersing the wafer in pure water or a solution of pH 7 or higher. Based on the difference or the difference in Haze between the etched part and the non-etched part, the protective property of the polymer can be evaluated inexpensively, simply and accurately. Moreover, if evaluation is performed using a plurality of types of polymers, the protective properties of the polymers can be relatively evaluated among the plurality of polymers.
以下、実施例及び比較例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to these.
［実施例１］
浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差（ΔＨａｚｅ）に基づいて、ポリマーＡ、ポリマーＢ、ポリマーＣの３種類のポリマーの保護性を評価した。
[Example 1]
Based on the difference (ΔHaze) between the haze of the immersion part and the haze of the non-immersion part, the protective properties of the three types of polymers A, B and C were evaluated.
（ポリマーの吸着）
ＨＦ洗浄により表面酸化膜を除去し、更に通常の仕上げ研磨を行った直径３００ｍｍのシリコンウェーハを用意し、最終仕上げ研磨にて各ポリマーを含む水溶液を染み込ませた布を用いて、荷重１０ｋＰａ、回転数１０ｒｐｍ、１０秒間にわたって研磨を行い、シリコンウェーハの表面に各ポリマーを吸着させた。なお、各ポリマーを含む水溶液は、１．０Ｌ／ｍｉｎで研磨定盤に供給した。
(Polymer adsorption)
A silicon wafer with a diameter of 300 mm prepared by removing the surface oxide film by HF cleaning and further subjected to normal finish polishing is prepared. Using a cloth soaked with an aqueous solution containing each polymer in the final finish polishing, a load of 10 kPa is rotated. Polishing was performed for several 10 rpm for 10 seconds, and each polymer was adsorbed on the surface of the silicon wafer. In addition, the aqueous solution containing each polymer was supplied to the polishing platen at 1.0 L / min.
（シリコンウェーハの浸漬）
純水を貯めたピット槽を用意し、各ポリマーを吸着させたシリコンウェーハをその中に浸漬させた。その際、浸漬部と非浸漬部が生じるよう水位を調整した。浸漬は、光による表面荒れを抑制するために暗闇中にて２４時間行った。
(Immersion of silicon wafer)
A pit tank storing pure water was prepared, and a silicon wafer adsorbing each polymer was immersed therein. At that time, the water level was adjusted so that an immersion part and a non-immersion part were generated. The immersion was performed for 24 hours in the dark in order to suppress surface roughness due to light.
（浸漬後のシリコンウェーハのＨａｚｅ測定）
表面に付着したポリマーを除去するため、ＳＣ１を用いて浸漬後のシリコンウェーハを洗浄した。次いで、ＫＬＡテンコール社製パーティクルカウンターＳＰ２を用いて浸漬部のＨａｚｅと非浸漬部のＨａｚｅを測定し、浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差（ΔＨａｚｅ）を求めた。結果を図５に示す。
(Haze measurement of silicon wafer after immersion)
In order to remove the polymer adhering to the surface, the silicon wafer after immersion was cleaned using SC1. Next, the haze of the immersion part and the haze of the non-immersion part were measured using a particle counter SP2 manufactured by KLA Tencor, and the difference (ΔHaze) between the haze of the immersion part and the haze of the non-immersion part was determined. The results are shown in FIG.
（比較用ウェーハのＨａｚｅの測定）
ポリマーの保護性を相対的に評価するために、表面酸化膜を除去していないシリコンウェーハ、及びＨＦ洗浄により表面酸化膜を除去しその後のポリマーの吸着は行っていないシリコンウェーハにおいても、上記と同様にシリコンウェーハの浸漬及び浸漬後のシリコンウェーハのＨａｚｅの測定を行い、浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差（ΔＨａｚｅ）を求めた。結果を図５に示す。
(Measurement of Haze of comparative wafer)
In order to relatively evaluate the protective property of the polymer, the silicon wafer from which the surface oxide film was not removed and the silicon wafer from which the surface oxide film was removed by HF cleaning and the subsequent polymer adsorption was not performed Similarly, the haze of the silicon wafer after immersion and the immersion of the silicon wafer was measured, and the difference (ΔHaze) between the haze of the immersion part and the haze of the non-immersion part was obtained. The results are shown in FIG.
［比較例１］
Ｃｕ故意汚染によるピット増加数に基づいて、ポリマーＡ、ポリマーＢ、ポリマーＣの３種類のポリマーの保護性を評価した。
[Comparative Example 1]
Based on the number of pits increased due to intentional Cu contamination, the protective properties of three types of polymers A, B and C were evaluated.
（ポリマーの吸着とＣｕ故意汚染によるピット増加数の測定）
実施例１と同様にして各ポリマーを吸着させたシリコンウェーハを用意し、Ｃｕを１ｐｐｍ添加した純水にシリコンウェーハを５分間浸漬させた（Ｃｕ故意汚染）後、ＳＣ１を用いて浸漬後のシリコンウェーハを洗浄し、ＫＬＡテンコール社製パーティクルカウンターＳＰ２を用いてピットの増加数を測定した。結果を図６に示す。
(Measurement of pit increase due to polymer adsorption and Cu intentional contamination)
A silicon wafer on which each polymer was adsorbed was prepared in the same manner as in Example 1, and the silicon wafer was immersed for 5 minutes in pure water to which 1 ppm of Cu was added (Cu intentional contamination), and then the silicon after immersion using SC1. The wafer was washed, and the number of pits increased was measured using a particle counter SP2 manufactured by KLA Tencor. The results are shown in FIG.
（比較用ウェーハのＣｕ故意汚染によるピット増加数の測定）
ポリマーの保護性を相対的に評価するために、表面酸化膜を除去していないシリコンウェーハ、及びＨＦ洗浄により表面酸化膜を除去しその後のポリマーの吸着は行っていないシリコンウェーハにおいても、上記と同様にＣｕ故意汚染及びピット増加数の測定を行った。結果を図６に示す。
(Measurement of the number of pit increase due to intentional Cu contamination of comparative wafer)
In order to relatively evaluate the protective property of the polymer, the silicon wafer from which the surface oxide film was not removed and the silicon wafer from which the surface oxide film was removed by HF cleaning and the subsequent polymer adsorption was not performed Similarly, the intentional contamination of Cu and the number of pit increases were measured. The results are shown in FIG.
図５に示されるように、実施例１の方法では、ポリマーＡを吸着させた場合は表面酸化膜を除去していない場合と同等レベルのΔＨａｚｅであり、ポリマーＢを吸着させた場合はポリマーＡを吸着させた場合よりもΔＨａｚｅが大きく、ポリマーＣを吸着させた場合はポリマーＢを吸着させた場合よりもΔＨａｚｅが大きく、ポリマーを吸着させていない場合はポリマーＣを吸着させた場合よりも大幅にΔＨａｚｅが大きい、という結果が得られた。このことから、ポリマー種によって面荒れの進行具合は異なっており、ポリマーＢ、Ｃを吸着させた場合は、ポリマーを吸着させていない場合と比べると浸漬による面荒れを大幅に抑制できているものの、ポリマーＡを吸着させた場合と比べると浸漬による面荒れが進んでいることが分かる。 As shown in FIG. 5, in the method of Example 1, when the polymer A was adsorbed, the ΔHaze was the same level as when the surface oxide film was not removed, and when the polymer B was adsorbed, the polymer A ΔHaze is larger than when adsorbing polymer, ΔHaze is greater when polymer C is adsorbed than when polymer B is adsorbed, and significantly greater than when polymer C is adsorbed when polymer is not adsorbed As a result, ΔHaze was large. From this, the progress of surface roughness varies depending on the polymer type, and when the polymers B and C are adsorbed, the surface roughness due to immersion can be greatly suppressed as compared with the case where the polymer is not adsorbed. It can be seen that the surface roughness due to immersion is more advanced than when the polymer A is adsorbed.
一方、図６に示されるように、比較例１の方法では、ポリマーＡを吸着させた場合は表面酸化膜を除去していない場合と同等レベルのピット数であり、ポリマーＢを吸着させた場合はポリマーＡを吸着させた場合よりもピット増加数が多く、ポリマーＣを吸着させた場合はポリマーＢを吸着させた場合よりもピット増加数が多く、ポリマーを吸着させていない場合はポリマーＣを吸着させた場合よりも大幅にピット増加数が多い、という結果が得られた。このことから、ポリマー種によってピットの発生具合は異なっており、ポリマーＢ、Ｃを吸着させた場合は、ポリマーを吸着させていない場合と比べるとＣｕ故意汚染によるピットの発生を大幅に抑制できているものの、ポリマーＡを吸着させた場合と比べるとＣｕ故意汚染によるピットの発生が起こっていることが分かる。なお、比較例１の方法では、実際にＣｕによる故意汚染を行っているため、分析に使用する設備（浸漬槽や洗浄槽）等の金属汚染が発生していた。 On the other hand, as shown in FIG. 6, in the method of Comparative Example 1, when the polymer A was adsorbed, the number of pits was the same level as when the surface oxide film was not removed, and when the polymer B was adsorbed Has more pit increases than when polymer A is adsorbed, and when polymer C is adsorbed there are more pit increases than when polymer B is adsorbed, and polymer C is adsorbed when no polymer is adsorbed. The result was that the number of pits increased significantly compared to the case of adsorption. From this, the pit generation condition varies depending on the polymer type, and when the polymers B and C are adsorbed, the generation of pits due to the intentional contamination of Cu can be significantly suppressed as compared with the case where the polymer is not adsorbed. However, compared with the case where the polymer A is adsorbed, it can be seen that pits are generated due to Cu intentional contamination. In addition, in the method of Comparative Example 1, since intentional contamination with Cu was actually performed, metal contamination of facilities (immersion tank and washing tank) used for analysis occurred.
上記の実施例１と比較例１の結果の比較から、エッチングによる面荒れ耐性の指標となる実施例１のΔＨａｚｅが、金属汚染耐性の指標となる比較例１のピット増加数と強く相関していることが分かる。つまり、実施例１のようにΔＨａｚｅを求めることによって、エッチングによる面荒れ耐性だけでなく、これと相関する金属汚染耐性も評価することができる。また、実施例１の方法では、Ｃｕによる故意汚染を行わないため、比較例１の方法のように分析に使用する設備等の金属汚染が発生する恐れもない。更に、実施例１の方法であれば、ポリマー種間で異なる保護性を相対的に比較することができ、また、表面酸化膜を除去していない場合やポリマーを吸着させていない場合と比較することで、ポリマーの保護性を相対的に評価することもできる。 From the comparison of the results of Example 1 and Comparative Example 1 above, ΔHaze of Example 1 which is an index of surface roughness resistance by etching strongly correlates with the number of pit increases of Comparative Example 1 which is an index of metal contamination resistance. I understand that. That is, by obtaining ΔHaze as in Example 1, it is possible to evaluate not only the surface roughness resistance due to etching but also the metal contamination resistance correlated therewith. Further, in the method of Example 1, since intentional contamination with Cu is not performed, there is no possibility that metal contamination of facilities used for analysis, etc., as in the method of Comparative Example 1 will occur. Furthermore, with the method of Example 1, it is possible to relatively compare different protective properties between polymer species, and to compare with the case where the surface oxide film is not removed or the case where the polymer is not adsorbed. Thus, the protective properties of the polymer can be relatively evaluated.
以上のことから、ΔＨａｚｅに基づいてポリマーの保護性を評価する本発明の評価方法であれば、シリコンウェーハ表面を保護するためのポリマーの保護性を安価かつ簡便に評価できることが明らかとなった。 From the above, it has been clarified that the protection method of the polymer for protecting the silicon wafer surface can be evaluated inexpensively and easily by the evaluation method of the present invention in which the protection property of the polymer is evaluated based on ΔHaze.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
１…ベアシリコン、 １ａ…浸漬部、 １ｂ…非浸漬部、 ２…純水。 DESCRIPTION OF SYMBOLS 1 ... Bare silicon, 1a ... Immersion part, 1b ... Non-immersion part, 2 ... Pure water.
Claims (3)
純水又は純水に任意のアルカリを溶解させたｐＨ７以上の溶液に、前記ポリマーにより表面が保護されたウェーハの一部又は全部を浸漬させ、該浸漬後のウェーハのＨａｚｅと浸漬前のウェーハのＨａｚｅとの差、又は前記浸漬後のウェーハの浸漬部のＨａｚｅと非浸漬部のＨａｚｅとの差に基づいて前記ポリマーの保護性を評価することを特徴とするポリマーの保護性評価方法。 A method for evaluating the protective properties of a polymer that protects the wafer surface by adsorbing to the wafer surface,
A part or all of the wafer whose surface is protected by the polymer is immersed in pure water or a solution of pH 7 or higher in which an arbitrary alkali is dissolved in pure water. The haze of the wafer after immersion and the wafer before immersion A method for evaluating the protective property of a polymer, comprising evaluating the protective property of the polymer based on a difference from Haze, or a difference between a haze in a dipped portion of the wafer after dipping and a haze in a non-dipped portion.
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| US20070148917A1 (en) * | 2005-12-22 | 2007-06-28 | Sumco Corporation | Process for Regeneration of a Layer Transferred Wafer and Regenerated Layer Transferred Wafer |
| JP2009019102A (en) * | 2007-07-11 | 2009-01-29 | Mitsui Chemicals Inc | Molded product for clean room and container |
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