JPH05138142A - Control method for sticking of fine particle in liquid - Google Patents
Control method for sticking of fine particle in liquidInfo
- Publication number
- JPH05138142A JPH05138142A JP20025291A JP20025291A JPH05138142A JP H05138142 A JPH05138142 A JP H05138142A JP 20025291 A JP20025291 A JP 20025291A JP 20025291 A JP20025291 A JP 20025291A JP H05138142 A JPH05138142 A JP H05138142A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- substance
- solution
- controlling
- adhesion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電子材料、磁性材料、
光学材料、セラミックスなど多くの製造プロセスにおい
て、各種金属、合金、セラミックスを含む無機物または
有機物を含む化合物の微粒子の分散制御及び付着制御を
する方法に係る。BACKGROUND OF THE INVENTION The present invention relates to electronic materials, magnetic materials,
The present invention relates to a method for controlling the dispersion and adhesion of fine particles of various metals, alloys, inorganic compounds including ceramics or compounds containing organic substances in many manufacturing processes such as optical materials and ceramics.
【０００２】特に、半導体装置の製造工程等において半
導体ウェハ等半導体基板の表面に微粒子が付着するのを
防止あるいは低減させる洗浄法に関する。In particular, the present invention relates to a cleaning method for preventing or reducing the adhesion of fine particles to the surface of a semiconductor substrate such as a semiconductor wafer in the manufacturing process of semiconductor devices.
【０００３】[0003]
【従来の技術】半導体ウェハ等の基板の表面に形成され
る集積回路は、近年ますます集積度が増加しており、そ
れにつれてパターンの線幅が微細化してきている。次期
１６ＭＤＲＡＭにおいて最小加工寸法は０．５μｍであ
り、その製造工程においてより微小な微粒子が製品の品
質や歩留まりの向上の障害になると考えられる。2. Description of the Related Art In recent years, the degree of integration of integrated circuits formed on the surface of a substrate such as a semiconductor wafer has been increasing, and the line width of patterns has become finer accordingly. The minimum processing size of the next 16 MDRAM is 0.5 μm, and it is considered that finer fine particles in the manufacturing process hinder the improvement of product quality and yield.
【０００４】従来、基板表面を洗浄する手段として、ア
ールシーエーレビュー３１（１９７０年）第１８７頁か
ら第２０６頁［ＲＣＡ Ｒｅｖｉｅｗ，３１（１９７
０）Ｐ．１８７〜２０６］で述べられているように、ア
ンモニア水と過酸化水素水の混合物を８０℃程度に加熱
し、これにウェハを浸漬する方法や、超純水中で、超音
波を加える方法がある。特に後者の超音波洗浄に関して
は通常の５０ｋＨｚではなく、ジャーナルオブエレクト
ロニックマテリアルズ第８巻（１９７９年）第８５５頁
から第８６４頁［Ｊ．Ｅｌｅｃ．Ｍａｔｅｒｉａｌｓ，
８（１９７９）Ｐ８５５〜８６４］で述べられているよ
うに８５０ｋＨｚの周波数のものを用いたり、特開昭６
０−１８７３８０で述べられているように超音波放射表
面と液面の距離を変化させたり、特開昭６１−１０１２
８３で述べられているように基本周波数に周波数変調を
行ったり、様々な工夫を施し実用に供している。Conventionally, as a means for cleaning the surface of a substrate, RCA Review 31 (1970), pages 187 to 206 [RCA Review, 31 (197).
0) P. 187-206], a method of heating a mixture of ammonia water and hydrogen peroxide solution to about 80 ° C. and immersing the wafer in it, or a method of applying ultrasonic waves in ultrapure water is used. is there. Especially for the latter ultrasonic cleaning, not the usual 50 kHz, but Journal of Electronic Materials Vol. 8 (1979) pp. 855 to 864 [J. Elec. Materials,
8 (1979) P855-864].
As described in JP-A-0-187380, the distance between the ultrasonic wave emitting surface and the liquid surface can be changed, or JP-A-61-1012.
As described in No. 83, the fundamental frequency is frequency-modulated or various measures are taken for practical use.
【０００５】[0005]
【発明が解決しようとする課題】前記集積回路における
集積度の高密度化により次期１６ＭＤＲＡＭにおける最
小加工寸法は０．５μｍであり、それにつれて、洗浄の
対象となっている微粒子の大きさも微小化し、０．０５
μｍの微粒子をも除去する必要があると考えられてい
る。Due to the higher integration density of the integrated circuit, the minimum processing size of the next 16M DRAM is 0.5 μm, and the size of the fine particles to be cleaned is also reduced accordingly. 0.05
It is considered that it is also necessary to remove fine particles of μm.
【０００６】微粒子が微小化するにつれて大気中におけ
る存在数が増加し、現在（４ＭＤＲＡＭ）対象となって
いる０．１３μｍの微粒子より０．０５μｍの微粒子は
数倍多く存在する。また、微粒子が微小化するにつれ
て、基板に付着しやすくなると考えられ、ますます微粒
子の洗浄技術の必要性が高まっているといえる。As the fine particles become finer, the number of them present in the atmosphere increases, and the fine particles of 0.05 μm are several times larger than the fine particles of 0.13 μm that are currently targeted (4MDRAM). Further, it is considered that the particles are more likely to adhere to the substrate as they become smaller, and thus it can be said that the need for a particle cleaning technique is increasing.
【０００７】しかし、超音波等機械的な力で基板から微
粒子を除去する従来法では、微粒子が微小化するにつれ
て、その質量や表面積が小さくなるので、１個あたりに
かかる機械的な力は小さくなり除去しにくくなる。ま
た、基板へのダメージも、半導体の集積度の向上に伴っ
て問題になってきている。そのため従来法では、微小化
した微粒子の除去はむずかしいと考えられる。However, in the conventional method of removing fine particles from the substrate by mechanical force such as ultrasonic waves, as the fine particles become finer, their mass and surface area become smaller, so that the mechanical force applied to each piece is small. It becomes difficult to remove. Further, damage to the substrate has become a problem as the degree of integration of semiconductors is improved. Therefore, it is considered difficult to remove the fine particles by the conventional method.
【０００８】本発明は、上記問題を解決するため発想を
転換し、基板への微粒子の付着を防止あるいは低減する
技術を提供するものである。The present invention provides a technique for changing the idea in order to solve the above problems and preventing or reducing the adhesion of fine particles to a substrate.
【０００９】[0009]
【課題を解決するための手段】本発明は、溶液中にある
微粒子のゼータ電位（表面電位）を制御できる物質を、
該溶液中に添加することにより、溶液中にある前記微粒
子の付着を防止あるいは低減する液中微粒子付着制御法
に関する。The present invention provides a substance capable of controlling the zeta potential (surface potential) of fine particles in a solution,
The present invention relates to a method for controlling the adhesion of fine particles in a liquid, which prevents or reduces the adhesion of the fine particles in the solution by adding it to the solution.
【００１０】図１に、本発明の基本概念図を示す。図１
（ａ）は、基板−微粒子間の距離とポテンシャルエネル
ギー（Ｗ）の関係を示したものであり、図１（ｂ）は、
基板１と微粒子２との間の表面電荷３により形成される
電気二重層による静電気反発力、図１（ｃ）は、基板１
と微粒子２との間のｖａｎ ｄｅｒ Ｗａａｌｓ力によ
る引力を示す概念図である。図１（ａ）に示すように、
液中では基板１と微粒子２との間のポテンシャルエネル
ギーＷは、ｖａｎ ｄｅｒ Ｗａａｌｓ力による引力
（ＶA）と電気二重層による静電気反発力（ＶR）の２つ
のポテンシャルの和（Ｗ＝ＶA＋ＶR）であり、このポテ
ンシャルの山を超えることにより基板に微粒子が付着す
ると考えられる。そこで、本発明は、このポテンシャル
の山を高くして、基板への微粒子の付着を低減させるた
めに基板及び微粒子の表面電位（ゼータ電位）を大きく
し静電気反発力を高めることに着目してなされたもので
ある。FIG. 1 shows a basic conceptual diagram of the present invention. Figure 1
1A shows the relationship between the distance between the substrate and the fine particles and the potential energy (W), and FIG. 1B shows
The electrostatic repulsion force due to the electric double layer formed by the surface charge 3 between the substrate 1 and the fine particles 2, FIG.
FIG. 3 is a conceptual diagram showing an attractive force due to a van der Waals force between particles and fine particles 2. As shown in FIG.
In the liquid, the potential energy W between the substrate 1 and the fine particles 2 is the sum of two potentials (W = VA + VR) of the attractive force (VA) due to the van der Waals force and the electrostatic repulsive force (VR) due to the electric double layer. It is considered that fine particles adhere to the substrate when the potential peaks are exceeded. Therefore, the present invention has been made paying attention to increasing the electrostatic potential by increasing the surface potential (zeta potential) of the substrate and the particles in order to increase the peak of this potential and reduce the adhesion of the particles to the substrate. It is a thing.
【００１１】図２に基板への微粒子の付着量と微粒子の
ゼータ電位の関係を示す。FIG. 2 shows the relationship between the amount of fine particles adhering to the substrate and the zeta potential of the fine particles.
【００１２】図２において、４はフッ化水素酸でエッチ
ング処理したシリコン（Ｓｉ）粒子（容積比でＨＦ：Ｈ
2Ｏ＝１：９９のフッ化水素酸に浸漬後フィルタで捕集
した微粒子。以降ベアＳｉ粒子という。）５は処理しな
いＳｉ粒子、６はポリスチレン粒子である。粒子の種類
によってゼータ電位が異なっており、また同じＳｉ粒子
でも表面状態によりゼータ電位の値が異なり、基板への
微粒子の付着量が異なっている。したがって、ゼータ電
位を制御することによって基板への微粒子の付着を防止
あるいは低減することができると考えられる。In FIG. 2, 4 is silicon (Si) particles etched by hydrofluoric acid (HF: H in volume ratio).
Fine particles collected by a filter after being immersed in hydrofluoric acid of 2 O = 1: 99. Hereinafter referred to as bare Si particles. ) 5 is untreated Si particles and 6 is polystyrene particles. The zeta potential differs depending on the type of particles, and even the same Si particles have different zeta potential values depending on the surface state, and the amount of fine particles attached to the substrate also differs. Therefore, it is considered that controlling the zeta potential can prevent or reduce the adhesion of fine particles to the substrate.
【００１３】また、基板と微粒子のゼータ電位は、一般
的には負であるが、まれにアルミナ基板とアルミナ粒子
の様に両者が正である場合もあり得る。ゼータ電位を制
御するとは、その絶対値を大きくすることを意味する。Further, the zeta potential of the substrate and the fine particles is generally negative, but in some cases, both may be positive like the alumina substrate and the alumina particles. Controlling the zeta potential means increasing its absolute value.
【００１４】本発明は、液中に特定の物質を添加するこ
とにより微粒子あるいは基板のゼータ電位を制御できる
という知見に基づいてなされたものである。The present invention was made based on the finding that the zeta potential of fine particles or a substrate can be controlled by adding a specific substance to a liquid.
【００１５】ここで、ゼータ電位と滑り面の関係につい
て簡単に述べる。Here, the relationship between the zeta potential and the sliding surface will be briefly described.
【００１６】微粒子が溶液中を移動する際、微粒子の周
囲には液体分子が数層吸着して移動していくものと考え
られる。このときの数層の液体分子とその周りの液体の
境界面を「滑り面」といい、この面の電位が上記したよ
うに微粒子の付着に関係している。（滑り面について
は、例えば北原文雄著「分散・乳化系の化学」（工学図
書１９７９年）第１０２頁に記されている。）一方ゼー
タ電位は電気泳動法により測定されるため、まさにこの
滑り面の電位を測定していることになる。（ゼータ電位
測定の詳細は後記の実施例に示した。）本発明ではゼー
タ電位、すなわち滑り面の電位を制御できる物質とし
て、アルコール、グリコール、アミン、アミド、アミノ
アルコール、アルデヒド、有機酸、エステル、ケトン及
び非イオン界面活性剤等の物質を液中に添加することが
有効であることを見出した。これらの物質は、その分子
内の電荷分布が一様ではなく、ある部分はやや正に、あ
る部分はやや負になっており、全体としてゼロとなって
いる。すなわち、これらの物質は、双極子モーメントを
持っている。そして、これらの物質により微粒子等のゼ
ータ電位が変化するのは、この電荷分布の不均一性が原
因であると考えられる。例えば、種々のアルコールを用
いた場合ゼータ電位の値は異なっており、これは以下の
ように分子内の電荷分布の不均一性により半定量的に説
明できる。It is considered that when the fine particles move in the solution, several layers of liquid molecules are adsorbed and moved around the fine particles. The boundary surface between several layers of liquid molecules and the surrounding liquid at this time is called a "sliding surface", and the electric potential of this surface is related to the adhesion of fine particles as described above. (The sliding surface is described in, for example, Fumio Kitahara, "Chemistry of Dispersion / Emulsion System" (Engineering Book, 1979), page 102.) On the other hand, since the zeta potential is measured by the electrophoresis method, this slippage is just what It means that the surface potential is being measured. (Details of the zeta potential measurement are shown in the examples below.) In the present invention, alcohol, glycol, amine, amide, aminoalcohol, aldehyde, organic acid, ester is used as a substance capable of controlling the zeta potential, that is, the potential of the sliding surface. It has been found that it is effective to add substances such as a ketone and a nonionic surfactant to the liquid. In these substances, the charge distribution in the molecule is not uniform, some parts are slightly positive, some parts are slightly negative, and the total is zero. That is, these materials have a dipole moment. It is considered that the non-uniformity of the charge distribution causes the zeta potential of the fine particles and the like to change due to these substances. For example, when various alcohols are used, the zeta potential values are different, which can be explained semi-quantitatively by the heterogeneity of the charge distribution in the molecule as follows.
【００１７】図３、図４は、微粒子表面に吸着したアル
コール分子について、量子力学に基づく理論計算により
求めたアルコールの分子内の電荷分布並びにゼータ電位
を示す。各アルコールの微粒子２への吸着状態は図３に
示す場合と図４に示す場合が考えられる。図３に示す場
合、滑り面の位置を微粒子２の表面より３〜４番目の原
子とすれば、その位置付近にある炭素原子の電荷の絶対
値が大きい程、ゼータ電位の絶対値は大きくなっている
ことが分かる。すなわち、アルコールが吸着した際、吸
着端より３〜４番目の原子付近に存在する局所的な電荷
の分布がゼータ電位の値に影響を与えると考えることが
できる。一方図４に示した場合、大きな負電荷を持つ酸
素原子の位置と滑り面との関係が各アルコールによって
異なっており、酸素原子が滑り面に近い程ゼータ電位の
絶対値は大きくなっていると考えることができる。した
がって、いずれの場合もゼータ電位の大きさはアルコー
ル分子内の電荷分布の不均一性によって決まるものと推
論される。FIGS. 3 and 4 show the charge distribution in the molecule and the zeta potential of the alcohol obtained by theoretical calculation based on quantum mechanics for the alcohol molecule adsorbed on the surface of the fine particles. The adsorption state of each alcohol on the fine particles 2 may be the case shown in FIG. 3 or the case shown in FIG. In the case shown in FIG. 3, assuming that the position of the sliding surface is the 3rd to 4th atom from the surface of the fine particles 2, the larger the absolute value of the electric charge of the carbon atom near that position, the larger the absolute value of the zeta potential becomes. I understand that. That is, when alcohol is adsorbed, it can be considered that the local distribution of charges existing in the vicinity of the third to fourth atoms from the adsorption end affects the value of the zeta potential. On the other hand, in the case shown in FIG. 4, the relationship between the position of the oxygen atom having a large negative charge and the sliding surface differs depending on the alcohol, and the closer the oxygen atom is to the sliding surface, the larger the absolute value of the zeta potential becomes. I can think. Therefore, in each case, it is inferred that the magnitude of the zeta potential depends on the nonuniformity of the charge distribution in the alcohol molecule.
【００１８】ただし、ゼータ電位を制御できる物質は基
板あるいは微粒子に吸着することが不可欠であり、１分
子中に−ＯＨ、−ＣＨＯ、−ＣＯＯＨ及び−ＮＨ2等の
親水性の基と炭化水素基からなる疎水性の基を持つ物質
である点が共通点であり、このことより微粒子への吸着
が起こるものと考えられる。However, it is essential that a substance capable of controlling the zeta potential is adsorbed on a substrate or fine particles, and a hydrophilic group such as --OH, --CHO, --COOH and --NH 2 and a hydrocarbon group are contained in one molecule. It has a common point that it is a substance having a hydrophobic group consisting of, and this is considered to cause adsorption to fine particles.
【００１９】また、ゼータ電位を制御できる上記物質
は、いずれもイオン解離しにくい物質である。イオン解
離しやすい物質を液中に添加する場合には、液中のイオ
ン濃度が高くなり微粒子の付着が起こりやすくなる。す
なわちゼータ電位を大きくしても微粒子付着防止効果が
充分に現われない場合がある。したがって、イオン解離
しにくい物質を用いることは本発明を実現する上で非常
に好ましい。Further, all of the above substances capable of controlling the zeta potential are substances which hardly dissociate into ions. When a substance that easily dissociates into ions is added to the liquid, the concentration of ions in the liquid increases, and the particles are likely to adhere. That is, even if the zeta potential is increased, the effect of preventing adhesion of fine particles may not be sufficiently exhibited. Therefore, it is very preferable to use a substance that is difficult to dissociate into ions in order to realize the present invention.
【００２０】したがって、イオン解離しにくく、１分子
中に親水性の基と疎水性の基を有する物質がゼータ電位
の制御に有効であることも理解できる。ただし、分子中
の電荷分布と滑り面との兼ね合いでゼータ電位制御効果
は異なってくる。すなわち、微粒子への疎水性の基の吸
着端から２〜６個目の原子のいずれか、あるいは複数個
の原子の電荷分布が負である物質が有効であることが容
易に理解できる。具体的にはそれらの原子が酸素原子、
ハロゲン原子及びチッ素原子等の電気陰性度の大きなも
のであるか、それらに結合する原子団が電子放出基ある
いは電気陰性度の大きな原子である場合である。またさ
らに複数種の物質を組合せることも有効である。Therefore, it can be understood that a substance which is less likely to undergo ionic dissociation and which has a hydrophilic group and a hydrophobic group in one molecule is effective for controlling the zeta potential. However, the effect of controlling the zeta potential differs depending on the balance between the charge distribution in the molecule and the slip surface. That is, it can be easily understood that a substance having a negative charge distribution of any of the atoms 2 to 6 or a plurality of atoms from the adsorption end of the hydrophobic group on the fine particles is effective. Specifically, those atoms are oxygen atoms,
This is the case where a halogen atom, a nitrogen atom, or the like has a large electronegativity, or the atomic group bonded to them is an electron emission group or an atom with a large electronegativity. It is also effective to combine a plurality of types of substances.
【００２１】図５は、分子長の異なる２種類以上の非イ
オン界面活性剤等の分子が微粒子の表面に吸着した状態
の概念図である。図５におけるように、微粒子２の表面
に分子長の異なるＣＨ3−Ｒ−Ｒ−Ｒ−Ｒ−ＯＨとＣＨ3
−Ｒ−Ｒ−Ｒ−ＯＨ（Ｒが、−（ＣＨ2）n−のときはア
ルコール、Ｒが−（ＣＨ2ＣＨ2Ｏ）m−、または−（Ｃ
Ｈ2）n−と−（ＣＨ2ＣＨ2Ｏ）m−の組合せであるとき
は非イオン界面活性剤である。n、mは５〜２０程度の整
数。）が吸着した場合には、密集して吸着した短いほう
の分子の分子末端が、疑似的粒子表面となり、すなわち
微粒子の滑り面は、短いほうの分子の末端の外側にシフ
トする。そして、長いほうの分子の親水性の基（電気陰
性度の大きい酸素原子を含む。）がちょうど滑り面付近
に位置することになるので、ゼータ電位を制御できる有
効な方法となる。FIG. 5 is a conceptual diagram showing a state in which two or more kinds of nonionic surfactants or the like having different molecular lengths are adsorbed on the surface of fine particles. As shown in FIG. 5, CH 3 —R—R—R—R—OH and CH 3 having different molecular lengths are formed on the surface of the fine particles 2.
-R-R-R-OH ( R is, - (CH 2) alcohol when n- of, R is - (CH 2 CH 2 O) m-, or - (C
H 2) n-and - (CH 2 CH 2 O) is when a m- combination is a nonionic surfactant. n and m are integers of about 5 to 20. ) Is adsorbed, the molecular ends of the shorter molecules that are densely adsorbed become pseudo particle surfaces, that is, the sliding surfaces of the fine particles shift to the outside of the ends of the shorter molecules. Since the hydrophilic group of the longer molecule (including an oxygen atom having a high electronegativity) is located just near the sliding surface, this is an effective method for controlling the zeta potential.
【００２２】図６（ａ）は、非イオン界面活性剤と比較
的分子鎖の短いアルコールを組合せて添加された場合
に、これらが微粒子２の表面に吸着した状態を示す概念
図である。また、図６（ｂ）と図６（ｃ）は、非イオン
界面活性剤等とアミノアルコールを組合せて添加された
場合に、これらが微粒子２の表面に吸着した状態を示す
概念図である。図６（ａ）〜図６（ｃ）において、Ｒは
図４の場合と同じである。FIG. 6 (a) is a conceptual diagram showing a state in which, when a nonionic surfactant and an alcohol having a relatively short molecular chain are combined and added, these are adsorbed on the surface of the fine particles 2. 6 (b) and 6 (c) are conceptual diagrams showing a state in which, when a nonionic surfactant or the like and an amino alcohol are added in combination, these are adsorbed on the surface of the fine particles 2. 6 (a) to 6 (c), R is the same as in FIG.
【００２３】このように、非イオン界面活性剤とアルコ
ールまたはアミノアルコールを組合せて用いる場合に
は、非イオン界面活性剤等の疎水性の基の部分に低分子
量のアルコールやアミノアルコールが吸着するためゼー
タ電位変化が起こると考えられる。そして、微粒子の種
類によっては、吸着量が多くなるため、ゼータ電位の変
化もより大きくなる。したがって、微粒子の付着防止効
果も大きくなる。As described above, when a nonionic surfactant and alcohol or aminoalcohol are used in combination, a low molecular weight alcohol or aminoalcohol is adsorbed on the hydrophobic group portion of the nonionic surfactant or the like. It is considered that zeta potential changes occur. Then, depending on the type of fine particles, the amount of adsorption increases, so that the change in zeta potential also increases. Therefore, the effect of preventing the adhesion of fine particles is also increased.
【００２４】非イオン界面活性剤等と組合せることによ
り付着防止効果が大きくなるものは、上記の他グリコー
ル、アミン、アミド、アルデヒド、有機酸、エステル及
びケトンなど１分子中に親水性の基と疎水性の基を持つ
物質である。In addition to the above-mentioned substances, those having a large anti-adhesion effect when combined with a nonionic surfactant or the like have a hydrophilic group in one molecule such as glycol, amine, amide, aldehyde, organic acid, ester and ketone. It is a substance having a hydrophobic group.
【００２５】上記のような物質の添加濃度は、物質の種
類にもよるが、一般的に、溶液に対して１０~7〜２５ｖ
ｏｌ％である。１０~7ｖｏｌ％以上の添加で効果があ
り、２５ｖｏｌ％より多くの添加は意味がない。The concentration of the above substance added depends on the kind of the substance, but is generally 10 to 7 to 25 v with respect to the solution.
ol%. Addition of 10 to 7 vol% or more is effective, and addition of more than 25 vol% is meaningless.
【００２６】最適添加濃度の範囲は、アルコールの場合
で０．１〜２．５ｖｏｌ％、アミノアルコールの場合で
１０~7〜１０~1ｖｏｌ％、有機酸の場合で１０~3〜１０
~1ｖｏｌ％、アルデヒドの場合で０．１〜１ｖｏｌ％、
ケトンの場合で０．１〜２ｖｏｌ％などである。The optimum addition concentration range is 0.1 to 2.5 vol% in the case of alcohol, 10 to 7 to 10 to 1 vol% in the case of amino alcohol, and 10 to 3 to 10 in the case of organic acid.
~ 1 vol%, in the case of aldehyde 0.1-1 vol%,
In the case of ketone, it is 0.1 to 2 vol%.
【００２７】[0027]
【作用】本発明によれば、ゼータ電位を制御できる物質
を溶液に添加することにより、溶液中の微粒子のゼータ
電位の絶対値が大きくなり、液中の基板と微粒子との間
の静電気反発力が増大する。その結果、微粒子と基板間
のポテンシャルエネルギーが高くなり、基板への微粒子
の付着を防止あるいは低減することが可能となる。According to the present invention, by adding a substance capable of controlling the zeta potential to the solution, the absolute value of the zeta potential of the fine particles in the solution becomes large, and the electrostatic repulsion force between the substrate and the fine particles in the liquid is increased. Will increase. As a result, the potential energy between the fine particles and the substrate increases, and it becomes possible to prevent or reduce the adhesion of the fine particles to the substrate.
【００２８】また同時に、微粒子同士の分散の向上ある
いは凝集を低減することも可能となる。At the same time, it becomes possible to improve the dispersion or reduce the agglomeration of the fine particles.
【００２９】[0029]
【実施例】先ず初めにゼータ電位測定法について述べ
る。EXAMPLES First, the zeta potential measuring method will be described.
【００３０】ゼータ電位は通常電気泳動法により求める
ことができる。電気泳動とは、液中に電場をかけたとき
表面電荷を持つ微粒子が移動する現象をいい、その微粒
子の移動速度を測定することによって、移動速度と比例
関係にある微粒子のゼータ電位を求めることができる。
本発明では、この原理に基づいたＰｅｎ Ｋｅｍ製ＬＡ
ＳＥＲ ＺＥＥ ＴＭ Ｍｏｄｅｌ ５０１により、微
粒子のゼータ電位の測定を行なった。The zeta potential can be usually determined by electrophoresis. Electrophoresis is a phenomenon in which particles with a surface charge move when an electric field is applied to the liquid. By measuring the moving speed of the particles, the zeta potential of the particles, which is proportional to the moving speed, is obtained. You can
In the present invention, LA manufactured by Pen Kem based on this principle is used.
The zeta potential of the fine particles was measured with a SER ZEE ™ Model 501.
【００３１】本発明の効果を確認するために、ポリスチ
レン粒子、Ｓｉ粒子、ＳｉＯ2粒子、Ｓｉ3Ｎ4粒子、Ｔ
ｉＯ2粒子、Ｃｒ粒子、Ｆｅ粒子、Ｃｕ粒子及びＷ粒子
を用いた。これらの粒子を用いたのは、単に粒子径の揃
ったものが容易に入手できるためであり、本発明の効果
はもちろんこれらの微粒子に限定されるものではない。In order to confirm the effect of the present invention, polystyrene particles, Si particles, SiO 2 particles, Si 3 N 4 particles, T
iO 2 particles, Cr particles, Fe particles, Cu particles and W particles were used. These particles are used simply because particles having a uniform particle size are easily available, and the effect of the present invention is not limited to these fine particles.
【００３２】ポリスチレン粒子は、Ｔｈｅ Ｄｏｗ Ｃ
ｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ製の粒子径１〜０．０
３８μｍのものを用いた。Ｓｉ粒子、ＳｉＯ2粒子、Ｓ
ｉ3Ｎ4粒子、ＴｉＯ2粒子、Ｃｒ粒子、Ｆｅ粒子、Ｃｕ
粒子及びＷ粒子は高純度化学製の粒子径１μｍのものを
用いた。Ｓｉ粒子については前処理しない場合と、容積
比が、ＨＦ：Ｈ2Ｏ＝１：９９のフッ化水素酸に１分間
エッチング処理した後実験に用いたベアＳｉ粒子の場合
とがある。またＰ型Ｓｉ粒子については、Ｐをドープし
た比抵抗９．００〜１２．０Ωｃｍの５インチのＰ型Ｓ
ｉウエハ（１００面）を粉砕して粒子径１μｍし前処理
しない場合と、容積比が、ＨＦ：Ｈ2Ｏ＝１：９９のフ
ッ化水素酸に１分間エッチング処理した後実験に用いた
ベアＰ型Ｓｉ粒子の場合とがある。さらにＰを高ドープ
した比抵抗０．００６Ωｃｍの５インチのＰ型Ｓｉウエ
ハ（１１１面）を粉砕して粒子径１μｍした高ドープＰ
型Ｓｉ粒子も用いた。Ｎ型Ｓｉ粒子についても同様に、
Ｂをドープした比抵抗８．００〜１２．０Ωｃｍの５イ
ンチのＮ型Ｓｉウエハ（１００面）を粉砕して粒子径１
μｍし前処理しない場合と、前処理したベアＰ型Ｓｉ粒
子及びＢを高ドープした比抵抗０．０１〜０．０１８Ω
ｃｍの５インチのＮ型Ｓｉウエハ（１１１面）を粉砕し
て粒子径１μｍした高ドープＮ型Ｓｉ粒子を用いた。The polystyrene particles are the The Dow C
Particle size 1-0.0 made by the chemical company
The one having a size of 38 μm was used. Si particles, SiO 2 particles, S
i 3 N 4 particles, TiO 2 particles, Cr particles, Fe particles, Cu
The particles and W particles used had a particle diameter of 1 μm manufactured by Kojundo Chemical. There is a case where Si particles are not pretreated, and a case where bare Si particles used in the experiment after being etched in hydrofluoric acid having a volume ratio of HF: H 2 O = 1: 99 for 1 minute. As for P-type Si particles, P-doped S-type of 5 inches having a specific resistance of 9.00 to 12.0 Ωcm.
The i-wafer (100 faces) was crushed to a particle size of 1 μm and not pretreated, and the bare wafer used in the experiment after etching for 1 minute in hydrofluoric acid with a volume ratio of HF: H 2 O = 1: 99. It may be P-type Si particles. Furthermore, a highly doped P having a high specific resistance of 0.006 Ωcm and a 5-inch P-type Si wafer (111 surface) pulverized to have a particle diameter of 1 μm.
Type Si particles were also used. Similarly for N-type Si particles,
A B-doped 5-inch N-type Si wafer (100 faces) having a specific resistance of 8.00 to 12.0 Ωcm was crushed to have a particle size of 1
μm and no pretreatment, and highly doped bare P-type Si particles and B highly doped specific resistance 0.01 to 0.018 Ω
A highly doped N-type Si particle having a particle diameter of 1 μm was obtained by crushing a 5-inch N-type Si wafer (111 surface).
【００３３】ゼータ電位の値は粒子の粒子径に依存しな
いと考えられ、上記粒子径での測定データは０．０５μ
ｍ程度の超微粒子においてもそのまま用いることができ
る。It is considered that the value of the zeta potential does not depend on the particle size of the particles, and the measured data with the above particle size is 0.05 μm.
Even ultrafine particles of about m can be used as they are.
【００３４】（実施例１）イオン解離しにくく、親水性
の基と疎水性の基を持つ物質のゼータ電位制御効果を表
１及び表２に示す。アルコール、アルデヒド、有機酸、
エステル及びケトン等広範囲な物質にゼータ電位制御効
果が認められた。このうち添加濃度とゼータ電位制御効
果の一例として、フッ化水素酸でエッチング処理したベ
アＳｉ粒子にエタノールを添加した場合について述べ
る。Example 1 Tables 1 and 2 show the effects of controlling the zeta potential of substances which are hard to undergo ion dissociation and have a hydrophilic group and a hydrophobic group. Alcohol, aldehyde, organic acid,
A wide range of substances such as esters and ketones were observed to have a zeta potential control effect. As an example of the added concentration and the effect of controlling the zeta potential, a case where ethanol is added to bare Si particles etched with hydrofluoric acid will be described.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】図７にエタノールの添加濃度とベアＳｉ粒
子のゼータ電位変化の関係を示す。エタノール添加前の
ベアＳｉ粒子は−２３．２ｍＶであったが、０．５ｖｏ
ｌ％のエタノールの添加によりＳｉ粒子のゼータ電位を
−４７．３ｍＶまで制御することができた。（図７には
記載していないが２５ｖｏｌ％（２０ｗｔ％）程度の添
加まで効果があった。）ゼータ電位の値が極小となる添
加濃度は物質によって異なるが、エタノール以外の物質
についても図７と同様の結果が得られた。表１及び表２
に、各種物質についてゼータ電位の値が極小となるとき
の添加濃度とそのときのゼータ電位の値を示した。FIG. 7 shows the relationship between the concentration of ethanol added and the change in zeta potential of bare Si particles. Bare Si particles before the addition of ethanol were −23.2 mV, but 0.5 vo
It was possible to control the zeta potential of Si particles to -47.3 mV by adding 1% ethanol. (Although not shown in FIG. 7, it was effective up to the addition of about 25 vol% (20 wt%).) The addition concentration at which the value of the zeta potential becomes the minimum differs depending on the substance, but for substances other than ethanol, it is also shown in FIG. Similar results were obtained. Table 1 and Table 2
Table 1 shows the added concentration and the value of the zeta potential when the value of the zeta potential was minimum for various substances.
【００３８】（実施例２）アミノアルコールに関して
は、より少ない添加濃度でより大きな効果が得られた。
各種アミノアルコールを添加したときのゼータ電位の変
化を表３に示す。(Example 2) With respect to amino alcohol, a larger effect was obtained with a smaller addition concentration.
Table 3 shows changes in zeta potential when various amino alcohols were added.
【００３９】[0039]
【表３】 [Table 3]
【００４０】また、２−アミノエタノールを添加した際
の添加濃度と１μｍのポリスチレン粒子のゼータ電位の
関係を図８に、またモノイソプロパノールアミンを添加
した際の添加濃度とゼータ電位の関係を図９に示す。ア
ミノアルコールの場合には実施例１の物質のようにゼー
タ電位の値が極小となることは少なく、図８及び図９に
示すように添加すればする程ゼータ電位の絶対値は大き
くなった。FIG. 8 shows the relationship between the addition concentration when 2-aminoethanol was added and the zeta potential of 1 μm polystyrene particles, and FIG. 9 shows the relationship between the addition concentration when monoisopropanolamine was added and the zeta potential. Shown in. In the case of amino alcohol, the value of zeta potential is unlikely to be the minimum as in the case of the substance of Example 1, and the absolute value of zeta potential becomes larger as it is added as shown in FIGS. 8 and 9.
【００４１】そして、アミノアルコールは１０~7ｍｏｌ
／ｌ（６×１０~7ｖｏｌ％）以上の添加でゼータ電位制
御に充分な効果が見られた。Amino alcohol is 10 to 7 mol.
Addition of at least 1 / l (6 × 10 to 7 vol%) showed a sufficient effect for controlling the zeta potential.
【００４２】（実施例３）表４にはハロゲン原子を含む
アルコール等を添加した際のゼータ電位の変化を示し
た。Example 3 Table 4 shows changes in the zeta potential when an alcohol containing a halogen atom or the like was added.
【００４３】[0043]
【表４】 [Table 4]
【００４４】ヘキサフルオロ−２−プロパノールや１
Ｈ，１Ｈ−ペンタフルオロプロパノールについては、ゼ
ータ電位を大きく変化させる効果のあることが分かっ
た。いずれもハロゲン原子を含まない物質よりも効果が
大きいことが分かる。Hexafluoro-2-propanol and 1
It was found that H, 1H-pentafluoropropanol has an effect of greatly changing the zeta potential. It can be seen that both are more effective than the substances containing no halogen atom.
【００４５】また、ハロゲンを含む界面活性剤の例とし
てペンタデカフルオロカプリル酸について検討した。ゼ
ータ電位を変化させる効果のあることがわかった。Further, pentadecafluorocaprylic acid was examined as an example of a surfactant containing halogen. It was found to have the effect of changing the zeta potential.
【００４６】（実施例４）表５にはチッ素原子を含む物
質を添加した際のゼータ電位の変化を示した。Example 4 Table 5 shows changes in zeta potential when a substance containing a nitrogen atom was added.
【００４７】[0047]
【表５】 [Table 5]
【００４８】ホルムアミドやＮ−メチルホルムアミドに
ついては、ゼータ電位を大きく変化させる効果のあるこ
とが分かった。いずれもチッ素原子を含まない物質より
も効果が大きいことが分かる。It was found that formamide and N-methylformamide have the effect of greatly changing the zeta potential. It can be seen that both are more effective than the substance containing no nitrogen atom.
【００４９】（実施例５） （Ｒ：−（ＣＨ2）n−，nは５〜２０程度の整数。）で
示される非イオン界面活性剤を合成し、ゼータ電位制御
効果について検討した。その結果を表６に示す。(Example 5) (R :-( CH 2) n-, n synthesizes a nonionic surfactant represented by an integer.) Of 5 to 20, were studied zeta potential control effect. The results are shown in Table 6.
【００５０】[0050]
【表６】 [Table 6]
【００５１】多くの粒子に対して効果のあることが分か
った。類似の構造を持つ界面活性剤についても同様の効
果が期待できる。It has been found to be effective for many particles. Similar effects can be expected for surfactants having a similar structure.
【００５２】（実施例６）分子長の異なる２種類の非イ
オン界面活性剤Ｉ：ＣＨ3（ＣＨ2）10ＣＨ2Ｏ（ＣＨ2Ｃ
Ｈ2Ｏ）12Ｈ及びII：ＣＨ3（ＣＨ2）14ＣＨ2Ｏ（ＣＨ2
ＣＨ2Ｏ）14Ｈを合成し、これらについてゼータ電位制
御効果について検討した。その結果を表７に示す。Example 6 Two kinds of nonionic surfactants I: CH 3 (CH 2 ) 10 CH 2 O (CH 2 C) having different molecular lengths
H 2 O) 12 H and II: CH 3 (CH 2 ) 14 CH 2 O (CH 2
CH 2 O) 14 H was synthesized, and the zeta potential control effect of these was examined. The results are shown in Table 7.
【００５３】[0053]
【表７】 [Table 7]
【００５４】多くの粒子に対して効果のあることが分か
った。類似の構造を持つ界面活性剤の組合せにも同様の
効果が期待できる。It has been found to be effective for many particles. The same effect can be expected with a combination of surfactants having a similar structure.
【００５５】（実施例７）非イオン界面活性剤ＣＨ
3（ＣＨ2）10ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）12Ｈとアルコー
ルを組合せて用いた例を表８、表９及び表１０に示す。Example 7 Nonionic Surfactant CH
Examples in which 3 (CH 2 ) 10 CH 2 O (CH 2 CH 2 O) 12 H and an alcohol are used in combination are shown in Tables 8, 9 and 10.
【００５６】[0056]
【表８】 [Table 8]
【００５７】[0057]
【表９】 [Table 9]
【００５８】[0058]
【表１０】 [Table 10]
【００５９】特に、アルコールだけでは効果の小さいＦ
ｅ粒子、Ｓｉ粒子及びＳｉＯ2粒子等にも大きな効果の
あることが分かった。またＳｉ粒子同様にＰ型Ｓｉ粒子
及びＮ型Ｓｉ粒子等不純物をドープしたＳｉ粒子にも大
きな効果があった。もちろんエタノール以外のアルコー
ルにも同様の効果が期待できる。Particularly, the effect of F, which is small with alcohol alone, is small.
It was found that e particles, Si particles, SiO 2 particles, etc. also have a great effect. Similar to Si particles, Si particles doped with impurities such as P-type Si particles and N-type Si particles also had a great effect. Of course, similar effects can be expected with alcohols other than ethanol.
【００６０】（実施例８）非イオン界面活性剤ＣＨ
3（ＣＨ2）10ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）12Ｈとアミノア
ルコールを組合せた例を表１１、表１２及び表１３に示
す。Example 8 Nonionic Surfactant CH
Examples of combinations of 3 (CH 2 ) 10 CH 2 O (CH 2 CH 2 O) 12 H and amino alcohol are shown in Tables 11, 12, and 13.
【００６１】[0061]
【表１１】 [Table 11]
【００６２】[0062]
【表１２】 [Table 12]
【００６３】[0063]
【表１３】 [Table 13]
【００６４】特に、アミノアルコールだけでは効果の小
さいＦｅ粒子、Ｓｉ粒子及びＳｉＯ2粒子等にも大きな
効果のあることが分かった。またＳｉ粒子同様にＰ型Ｓ
ｉ粒子及びＮ型Ｓｉ粒子等不純物をドープしたＳｉ粒子
にも大きな効果があった。In particular, it has been found that Fe particles, Si particles, SiO 2 particles, etc., which have a small effect only with amino alcohol, have a great effect. Also, like Si particles, P type S
There was a great effect on Si particles doped with impurities such as i particles and N-type Si particles.
【００６５】（実施例９）本発明による微粒子の付着防
止効果を以下の手順により確認した。図１０に示すよう
に、０．０３８μｍのポリスチレン粒子を液槽９の超純
水中に分散し（微粒子濃度は５×１０11個／ｍ3に調
整）、４インチＳｉウエハ８を一定時間浸漬した。次い
で、これを液槽９中より引き上げてスピンナー乾燥し、
電子顕微鏡（ＳＥＭ）により付着ポリスチレン粒子数を
測定した。浸漬時間と付着数の関係を図１１の１０とし
て示す。浸漬時間とともに付着数は増加することが分か
った。次に、２−アミノエタノールを６×１０~5ｖｏｌ
％加えた後、同様にして付着実験を行ない、得られた結
果を同じく図１１の１１として示す。ほとんど付着は見
られなかった。Example 9 The effect of preventing the adhesion of fine particles according to the present invention was confirmed by the following procedure. As shown in FIG. 10, 0.038 μm polystyrene particles were dispersed in ultrapure water in the liquid tank 9 (fine particle concentration was adjusted to 5 × 10 11 particles / m 3 ), and the 4-inch Si wafer 8 was immersed for a certain period of time. did. Next, this is pulled up from the liquid tank 9 and spinner dried,
The number of attached polystyrene particles was measured by an electron microscope (SEM). The relationship between the immersion time and the number of deposits is shown as 10 in FIG. It was found that the number of deposits increased with the immersion time. Next, 2-aminoethanol is added at 6 × 10 to 5 vol.
%, The adhesion test was conducted in the same manner, and the obtained result is also shown as 11 in FIG. Almost no adhesion was seen.
【００６６】また、２−アミノエタノールの代りにエタ
ノールを添加した場合は、付着量が３分の１程度に減少
した（図１２の１２） （実施例１０）次に０．０３８μｍポリスチレン粒子を
用いた同様の付着実験を、塩酸を加え溶液の水素イオン
濃度を調整して行なった。ｐＨ＝３での浸漬時間と付着
数の関係は超純水中での結果と同じで１１図と同様であ
った。すなわち浸漬時間とともに付着数は増加し、２−
アミノエタノールを６×１０~5ｖｏｌ％加えることによ
りほとんど付着は見られなかった。When ethanol was added instead of 2-aminoethanol, the adhered amount was reduced to about one third (12 in FIG. 12) (Example 10) Next, 0.038 μm polystyrene particles were used. The same adhesion experiment was performed by adding hydrochloric acid to adjust the hydrogen ion concentration of the solution. The relationship between the immersion time at pH = 3 and the number of deposits was the same as the result in ultrapure water and was the same as in FIG. That is, the number of adhesion increases with the immersion time,
Almost no adhesion was observed by adding 6 × 10 5 vol% of aminoethanol.
【００６７】（実施例１１）次に０．２μｍポリスチレ
ン粒子を用いて同様の付着実験を行なった。ただし、付
着粒子数の測定には光学顕微鏡を用いた。０．２μｍ粒
子は超純水中ではほとんど付着が見られないので、塩酸
を加え溶液の水素イオン濃度を調整して実験を行なっ
た。図１３の１３として示すようにｐＨ３程度より酸性
が大きくなると、０．２μｍ粒子は付着するようにな
る。（微粒子濃度は４×１０12個／ｍ3とし、ウエハを
１０分間浸漬した。）２−アミノエタノールを６×１０
~5ｖｏｌ％加えたところ、図１３の１４として示すよう
に付着の起こる水素イオン濃度は変化した。すなわち、
２−アミノエタノールの添加によりあるｐＨで起きてい
た付着を防止できることを示している。Example 11 Next, the same adhesion experiment was conducted using 0.2 μm polystyrene particles. However, an optical microscope was used to measure the number of adhered particles. Since particles of 0.2 μm hardly adhere to ultrapure water, experiments were conducted by adding hydrochloric acid to adjust the hydrogen ion concentration of the solution. As shown as 13 in FIG. 13, when the acidity becomes higher than about pH 3, 0.2 μm particles adhere. (The particle concentration was set to 4 × 10 12 particles / m 3 and the wafer was immersed for 10 minutes.) 2-aminoethanol 6 × 10
When ~ 5 vol% was added, the hydrogen ion concentration at which adhesion occurred changed as shown as 14 in FIG. That is,
It is shown that the addition of 2-aminoethanol can prevent the adhesion occurring at a certain pH.
【００６８】（実施例１２）次に１μｍポリスチレン粒
子を用いて同様の付着実験を行なった。ただし、付着粒
子数の測定には光学顕微鏡を用いた。１μｍ粒子は超純
水中ではほとんど付着が見られないので、塩酸を加え溶
液の水素イオン濃度を調整して実験を行なった。図１４
の１５として示すようにｐＨ２．２程度より酸性が大き
くなると、１μｍ粒子は付着するようになる。（微粒子
濃度は５×１０13個／ｍ3とし、ウエハを１０分間浸漬
した。）２−アミノエタノールを６×１０~5ｖｏｌ％加
えたところ、図１４の１６として示すように付着の起こ
る水素イオン濃度は変化した。すなわち、２−アミノエ
タノールの添加によりあるｐＨで起きていた付着を防止
できること、すなわち、より酸性の高い領域まで付着を
防止できることを示している。Example 12 Next, the same adhesion experiment was conducted using 1 μm polystyrene particles. However, an optical microscope was used to measure the number of adhered particles. Almost no adhesion of 1 μm particles was observed in ultrapure water, so experiments were conducted by adding hydrochloric acid to adjust the hydrogen ion concentration of the solution. 14
As shown as No. 15, when the acidity becomes higher than about pH 2.2, 1 μm particles are attached. (The particle concentration was set to 5 × 10 13 particles / m 3 and the wafer was immersed for 10 minutes.) When 6 × 10 to 5 vol% of 2-aminoethanol was added, hydrogen was generated as shown by 16 in FIG. The ion concentration changed. That is, it is shown that the addition of 2-aminoethanol can prevent the adhesion that has occurred at a certain pH, that is, the adhesion can be prevented even in a region having a higher acidity.
【００６９】なお、アルカリ側でも対称的に効果があ
り、２−アミノエタノールの添加により、付着が生じる
領域をよりアルカリ性の高いところまでずらすことがで
きる。It should be noted that there is a symmetrical effect on the alkaline side as well, and the addition of 2-aminoethanol makes it possible to shift the region where adhesion occurs to a more alkaline region.
【００７０】（実施例１３）次に容積比でＨＦ：Ｈ2Ｏ
＝１：９９のフッ化水素酸を調整して粒子径１μｍのベ
アＳｉ粒子を分散させ、同様の付着実験を行なった。
（微粒子濃度は５×１０13個／ｍ3に調整した。）図１
５の１７に示すように浸漬時間と共に付着数は増加する
ことが分かった。次に、実施例７で用いた非イオン界面
活性剤１０~6ｍｏｌ／ｌと２−アミノエタノール６×１
０~5ｖｏｌ％を加えた後、同様にして付着実験を行なっ
た。そして、得られた結果を同じく図１５の１８に示
す。ほとんど付着は見られなくなった。(Example 13) Next, the volume ratio of HF: H 2 O was changed.
= 1:99 of hydrofluoric acid was prepared to disperse bare Si particles having a particle diameter of 1 µm, and the same adhesion experiment was performed.
(The fine particle concentration was adjusted to 5 × 10 13 particles / m 3 ).
As shown in 17 of No. 5, it was found that the number of deposits increased with the immersion time. Next, 10 to 6 mol / l of the nonionic surfactant used in Example 7 and 6 × 1 of 2-aminoethanol were used.
After adding 0 to 5 vol%, an adhesion experiment was conducted in the same manner. The obtained results are also shown at 18 in FIG. Almost no adhesion was seen.
【００７１】（実施例１４）次に超純水中に粒子径１μ
ｍのＳｉ粒子を分散させ、同様の付着実験を行なった。
（Ｓｉ粒子はフッ化水素酸でエッチング処理せず、微粒
子濃度は５×１０13個／ｍ3に調整した。ウエハは１０
分間浸漬した。）図１６の１９として示すようにｐＨ
２．２程度より酸性が大きくなると、１μｍ粒子は付着
するようになる。実施例７で用いた非イオン界面活性剤
１０~6ｍｏｌ／ｌと２−アミノエタノールを６×１０~5
ｖｏｌ％加えたところ、図１６の２０として示すように
付着の起こる水素イオン濃度はより酸性側に変化した。
すなわち、２−アミノエタノールの添加によりあるｐＨ
で起きていた付着を防止できることが分かった。(Example 14) Next, the particle diameter was 1 μm in ultrapure water.
m Si particles were dispersed and the same adhesion experiment was performed.
(Si particles were not subjected to etching treatment with hydrofluoric acid, and the particle concentration was adjusted to 5 × 10 13 particles / m 3 .
Soaked for a minute. ) As shown as 19 in FIG.
If the acidity becomes larger than about 2.2, 1 μm particles will adhere. The nonionic surfactant used in Example 7 and 10 to 6 mol / l and 2-aminoethanol were added to 6 × 10 to 5 respectively.
When vol% was added, the hydrogen ion concentration at which adhesion occurred changed to a more acidic side, as indicated by 20 in FIG.
That is, a certain pH is obtained by adding 2-aminoethanol.
It was found that it was possible to prevent the adhesion that had occurred in.
【００７２】（実施例１５）次に超純粋中に粒子径１μ
ｍのＳｉＯ2粒子を分散させ、同様の付着実験を行なっ
た。（微粒子濃度は５×１０13個／ｍ3に調整し、ウエ
ハを１０分間浸漬した。）図１７の２１として示すよう
にｐＨ２．２程度より酸性が大きくなると、１μｍ粒子
は付着するようになる。実施例７で用いた非イオン界面
活性剤１０~6ｍｏｌ／ｌと２−アミノエタノールを６×
１０~5ｖｏｌ％加えたところ、図１７の２２として示す
ように付着の起こる水素イオン濃度はより酸性側に変化
した。すなわち、２−アミノエタノールの添加によりあ
るｐＨで起きていた付着を防止できることが分かった。(Example 15) Next, the particle size was 1 μm in ultrapure.
The SiO 2 particles of m were dispersed and the same adhesion experiment was conducted. (The fine particle concentration was adjusted to 5 × 10 13 particles / m 3 and the wafer was immersed for 10 minutes.) As shown by 21 in FIG. 17, when the acidity becomes higher than about pH 2.2, 1 μm particles adhere. .. The nonionic surfactant used in Example 7 (10 to 6 mol / l) and 2-aminoethanol (6 ×) were added.
When 10 to 5 vol% was added, the hydrogen ion concentration at which adhesion occurred changed to a more acidic side, as indicated by 22 in FIG. That is, it was found that the addition of 2-aminoethanol can prevent the adhesion that has occurred at a certain pH.
【００７３】（実施例１６）次に、超純水中に粒子径１
μｍのＦｅ粒子を分散させ、同様の付着実験を行なっ
た。（微粒子濃度は５×１０13個／ｍ3に調整し、ウエ
ハを１０分間浸漬した。）図１８の２３として示すよう
にｐＨ３程度より酸性が大きくなると、１μｍ粒子は付
着するようになる。実施例７で用いた非イオン界面活性
剤１０~6ｍｏｌ／ｌと２−アミノエタノールを６×１０
~5ｖｏｌ％加えたところ、図１８の２４として示すよう
に付着の起こる水素イオン濃度は変化した。すなわち、
２−アミノエタノールの添加によりあるｐＨで起きてい
た付着を防止できることが分かった。(Example 16) Next, a particle size of 1 was added to ultrapure water.
Fe particles of μm were dispersed, and the same adhesion experiment was performed. (The fine particle concentration was adjusted to 5 × 10 13 particles / m 3 and the wafer was immersed for 10 minutes.) As shown as 23 in FIG. 18, when the acidity is higher than about pH 3, 1 μm particles are attached. The nonionic surfactant used in Example 7 (10 to 6 mol / l) and 2-aminoethanol (6 × 10 6) were added.
When ~ 5 vol% was added, the hydrogen ion concentration at which adhesion occurred changed as shown by 24 in FIG. That is,
It was found that the addition of 2-aminoethanol can prevent the adhesion that had occurred at a certain pH.
【００７４】（実施例１７）次に２−アミノエタノール
の添加濃度と付着防止効果の関係について検討した。１
μｍのポリスチレン粒子を分散させ、同様の付着実験を
行なった。（微粒子濃度は５×１０13個／ｍ3に調整し
た。）図１９の２５として示すようにｐＨ２．２程度よ
り酸性が大きくなると、１μｍ粒子は付着するようにな
る。２−アミノエタノールを６×１０~5ｖｏｌ％加えた
ところ、図１９の２６として示すように付着の起こる水
素イオン濃度は変化した。２−アミノエタノールの添加
濃度を６×１０~3ｖｏｌ％とすると、図１９の２７とし
て示すように付着の起こる水素イオン濃度はさらに小さ
くなり、付着防止効果がより大きくなることが明らかに
なった。すなわち、２−アミノエタノールの添加濃度が
多くなることにより微粒子のゼータ電位の絶対値が大き
くなり、それだけ付着防止効果が大きくなったと考えら
れる。したがって他の粒子に対しても添加濃度を多くす
ることにより同様に効果が期待できる。(Example 17) Next, the relationship between the concentration of 2-aminoethanol added and the anti-adhesion effect was examined. 1
The same adhesion experiment was conducted by dispersing polystyrene particles of μm. (The fine particle concentration was adjusted to 5 × 10 13 particles / m 3 ). As shown as 25 in FIG. 19, when the acidity becomes higher than about pH 2.2, 1 μm particles adhere. When 6 × 10 to 5 vol% of 2-aminoethanol was added, the hydrogen ion concentration at which adhesion occurred changed as indicated by 26 in FIG. It was revealed that when the addition concentration of 2-aminoethanol was 6 × 10 to 3 vol%, the hydrogen ion concentration at which the adhesion occurred was further reduced and the adhesion prevention effect was further increased, as indicated by 27 in FIG. .. That is, it is considered that the absolute value of the zeta potential of the fine particles increased due to the increase in the concentration of 2-aminoethanol added, and the anti-adhesion effect increased accordingly. Therefore, similar effects can be expected for other particles by increasing the addition concentration.
【００７５】（実施例１８）次に容積比でＨＦ：Ｈ2Ｏ
＝１：９９のフッ化水素酸を調整して粒子径１μｍのＳ
ｉ粒子を分散させ、同様の付着実験を行なった。（粒子
濃度は５×１０13個／ｍ3に調整。）図２０に示すよう
に浸漬時間と共に付着数は増加することが分かった。次
に、実施例７で用いた非イオン界面活性剤１０~7ｍｏｌ
／ｌとｍ−アミノフェノールを１ｖｏｌ％を加えた後、
同様にして付着実験を行ない、得られた結果を同じく図
２０の２９に示す。ほとんど付着は見られなかった。(Embodiment 18) Next, in volume ratio, HF: H 2 O
= 1: 99 of hydrofluoric acid is prepared and S of particle diameter 1 μm is prepared.
The i particles were dispersed and the same adhesion experiment was performed. (The particle concentration was adjusted to 5 × 10 13 particles / m 3 ). As shown in FIG. 20, it was found that the number of deposits increased with the immersion time. Next, 10 to 7 mol of the nonionic surfactant used in Example 7
/ L and 1-vol% of m-aminophenol were added,
An adhesion experiment was conducted in the same manner, and the obtained results are also shown at 29 in FIG. Almost no adhesion was seen.
【００７６】（実施例１９）次に容積比でＨＦ：Ｈ2Ｏ
＝１：９９のフッ化水素酸を調整して粒子径１μｍのＳ
ｉ粒子を分散させ、同様の付着実験を行なった。（粒子
濃度は５×１０13個／ｍ3に調整した。）図２１に示す
ように浸漬時間と共に付着数は増加することが分かっ
た。次に、実施例７で用いた非イオン界面活性剤１０~7
ｍｏｌ／ｌとホルムアミド０．５ｖｏｌ％を加えた後、
同様にして付着実験を行ない、得られた結果を同じく図
２１の３１に示す。ほとんど付着は見られなかった。(Example 19) Next, the volume ratio of HF: H 2 O was changed.
= 1: 99 of hydrofluoric acid is prepared and S of particle diameter 1 μm is prepared.
The i particles were dispersed and the same adhesion experiment was performed. (The particle concentration was adjusted to 5 × 10 13 particles / m 3. ) As shown in FIG. 21, it was found that the number of adhered particles increased with the immersion time. Next, the nonionic surfactants 10 to 7 used in Example 7 were used.
After adding mol / l and 0.5 vol% formamide,
An adhesion experiment was conducted in the same manner, and the obtained results are also shown at 31 in FIG. Almost no adhesion was seen.
【００７７】（実施例２０）次に容積比でＨＦ：Ｈ2Ｏ
＝１：９９のフッ化水素酸を調整して粒子径１μｍのＳ
ｉ粒子を分散させ、同様の付着実験を行なった。（粒子
濃度は５×１０13個／ｍ3に調整した。）図２２に示す
ように浸漬時間と共に付着数は増加することが分かっ
た。次に、実施例７で用いた非イオン界面活性剤１０~7
ｍｏｌ／ｌとベンジルアミン１０~5ｍｏｌ／ｌを加えた
後、同様にして付着実験を行ない、得られた結果を同じ
く図２２の３３に示す。ほとんど付着は見られなかっ
た。(Example 20) Next, the volume ratio of HF: H 2 O was changed.
= 1: 99 of hydrofluoric acid is prepared and S of particle diameter 1 μm is prepared.
The i particles were dispersed and the same adhesion experiment was performed. (The particle concentration was adjusted to 5 × 10 13 particles / m 3. ) As shown in FIG. 22, it was found that the number of deposits increased with the immersion time. Next, the nonionic surfactants 10 to 7 used in Example 7 were used.
After adding mol / l and benzylamine 10 to 5 mol / l, an adhesion experiment was conducted in the same manner, and the obtained result is also shown in 33 of FIG. Almost no adhesion was seen.
【００７８】以上の付着実験により、本発明で述べたゼ
ータ電位の制御が微粒子の付着防止や低減に有効である
ことが実証された。From the above adhesion experiments, it was proved that the control of the zeta potential described in the present invention is effective for preventing and reducing the adhesion of fine particles.
【００７９】（実施例２１）本発明を実施するための洗
浄システムの一例を図２３に示す。図２３において、超
純水製造部３４で製造された超純水と、ゼータ電位制御
物質貯蔵部３５から混合量調節器３６を介して供給され
るゼータ電位制御物質が、洗浄槽３７に送られて混合さ
れ、Ｓｉウエハ搬送系３８から洗浄槽３７に運ばれるＳ
ｉウエハの洗浄に用いられる。(Embodiment 21) FIG. 23 shows an example of a cleaning system for carrying out the present invention. In FIG. 23, the ultrapure water produced in the ultrapure water production unit 34 and the zeta potential control substance supplied from the zeta potential control substance storage unit 35 via the mixing amount adjuster 36 are sent to the cleaning tank 37. S that are mixed together and carried from the Si wafer transfer system 38 to the cleaning tank 37.
Used for cleaning i-wafers.
【００８０】[0080]
【発明の効果】本発明によれば、液中における微粒子の
付着を防止及び低減することができるため、半導体装
置、薄膜デバイス、ディスク等のエレクトロニクス部品
の歩留まり高めることができ、低コストで上記製品を製
造することができる。According to the present invention, since the adhesion of fine particles in a liquid can be prevented and reduced, the yield of electronic parts such as semiconductor devices, thin film devices and disks can be increased, and the above products can be manufactured at low cost. Can be manufactured.
【００８１】また同時に、微粒子同士の分散の向上ある
いは凝集を低減することも可能となる。At the same time, it becomes possible to improve the dispersion or reduce the aggregation of the fine particles.
【図１】図１は、本発明に係る基板−微粒子間の距離と
ポテンシャルエネルギーの関係を示す図である。FIG. 1 is a diagram showing a relationship between a distance between a substrate and fine particles and potential energy according to the present invention.
【図２】図２は、微粒子のゼータ電位と微粒子付着数の
関係を示す図である。FIG. 2 is a diagram showing the relationship between the zeta potential of fine particles and the number of fine particles attached.
【図３】図３は、微粒子表面に吸着したアルコール分子
の電荷分布と滑り面の電位を示す図である。FIG. 3 is a diagram showing the charge distribution of alcohol molecules adsorbed on the surface of fine particles and the potential on the sliding surface.
【図４】図４は、微粒子表面に吸着したアルコール分子
の電荷分布と滑り面の電位を示す図である。FIG. 4 is a diagram showing the charge distribution of alcohol molecules adsorbed on the surface of fine particles and the potential on the sliding surface.
【図５】図５は、微粒子表面に吸着した非イオン界面活
性剤分子またはアルコール分子を示す図。FIG. 5 is a view showing nonionic surfactant molecules or alcohol molecules adsorbed on the surface of fine particles.
【図６】図６（ａ），図６（ｂ）及び図６（ｃ）は、非
イオン界面活性剤とアルコールを組合せて添加した場合
の吸着状態を示す図である。FIG. 6 (a), FIG. 6 (b) and FIG. 6 (c) are diagrams showing adsorption states when a nonionic surfactant and an alcohol are added in combination.
【図７】図７は、エタノールの添加濃度とベアＳｉ粒子
のゼータ電位の関係を示す図である。FIG. 7 is a diagram showing the relationship between the concentration of ethanol added and the zeta potential of bare Si particles.
【図８】図８は、２−アミノエタノールの添加濃度とポ
リスチレン粒子のゼータ電位の関係を示す図である。FIG. 8 is a graph showing the relationship between the concentration of 2-aminoethanol added and the zeta potential of polystyrene particles.
【図９】図９は、モノイソプロパノールアミンの添加濃
度と微粒子のゼータ電位の関係を示す図である。FIG. 9 is a graph showing the relationship between the concentration of monoisopropanolamine added and the zeta potential of fine particles.
【図１０】図１０は、４インチＳｉウエハを微粒子含有
超純水溶液に浸漬して取り出す行程図である。FIG. 10 is a process diagram of immersing a 4-inch Si wafer in an ultrapure aqueous solution containing fine particles and taking it out.
【図１１】図１１は、ウエハの浸漬時間と微粒子付着数
との関係を示すグラフである。FIG. 11 is a graph showing the relationship between the immersion time of a wafer and the number of adhered fine particles.
【図１２】図１２は、ウエハの浸漬時間と微粒子付着数
との関係を示すグラフである。FIG. 12 is a graph showing the relationship between the immersion time of a wafer and the number of adhered fine particles.
【図１３】図１３は、水素イオン濃度と微粒子付着数の
関係を示す図である。FIG. 13 is a diagram showing the relationship between hydrogen ion concentration and the number of adhered fine particles.
【図１４】図１４は、水素イオン濃度と微粒子付着数の
関係を示す図である。FIG. 14 is a diagram showing a relationship between hydrogen ion concentration and the number of adhered fine particles.
【図１５】図１５は、ウエハの浸漬時間と微粒子付着数
との関係を示すグラフである。FIG. 15 is a graph showing the relationship between the immersion time of a wafer and the number of adhered fine particles.
【図１６】図１６は、水素イオン濃度と微粒子付着数の
関係を示す図である。FIG. 16 is a diagram showing the relationship between the hydrogen ion concentration and the number of adhered fine particles.
【図１７】図１７は、水素イオン濃度と微粒子付着数の
関係を示す図である。FIG. 17 is a diagram showing the relationship between the hydrogen ion concentration and the number of attached fine particles.
【図１８】図１８は、水素イオン濃度と微粒子付着数の
関係を示す図である。FIG. 18 is a diagram showing the relationship between the hydrogen ion concentration and the number of adhered fine particles.
【図１９】図１９は、水素イオン濃度と微粒子付着数の
関係を示す図である。FIG. 19 is a diagram showing the relationship between hydrogen ion concentration and the number of adhered fine particles.
【図２０】図２０は、ウエハの浸漬時間と微粒子付着数
の関係を示す図である。FIG. 20 is a diagram showing the relationship between the immersion time of a wafer and the number of adhered fine particles.
【図２１】図２１は、ウエハの浸漬時間と微粒子付着数
の関係を示す図である。FIG. 21 is a diagram showing the relationship between the immersion time of a wafer and the number of adhered fine particles.
【図２２】図２２は、ウエハの浸漬時間と微粒子付着数
の関係を示す図である。FIG. 22 is a diagram showing the relationship between the immersion time of a wafer and the number of adhered fine particles.
【図２３】図２３は、本発明に係る洗浄システムの一例
を示す図である。FIG. 23 is a diagram showing an example of a cleaning system according to the present invention.
１…基板、２…微粒子、３…表面電荷、４…ベアＳｉ粒
子、５…Ｓｉ粒子、６…ポリスチレン粒子、７…滑り
面、８…４インチＳｉウエハ、９…液槽、１０…無添加
の場合、１１…２−アミノエタノールを６×１０~5ｖｏ
ｌ％添加した場合、１２…エタノールを１ｖｏｌ％添加
した場合、１３…塩酸を添加した場合、１４…２−アミ
ノエタノールを６×１０~5ｖｏｌ％添加した場合、１５
…塩酸を添加した場合、１６…２−アミノエタノールを
６×１０~5ｖｏｌ％添加した場合、１７…無添加の場
合、１８…非イオン界面活性剤１０~6ｍｏｌ／ｌと２−
アミノエタノールを６×１０~5ｖｏｌ％添加した場合、
１９…無添加の場合、２０…非イオン界面活性剤１０~6
ｍｏｌ／ｌと２−アミノエタノールを６×１０~5ｖｏｌ
％添加した場合、２１…無添加の場合、２２…非イオン
界面活性剤１０~6ｍｏｌ／ｌと２−アミノエタノールを
６×１０~5ｖｏｌ％添加した場合、２３…無添加の場
合、２４…非イオン界面活性剤１０~6ｍｏｌ／ｌと２−
アミノエタノールを６×１０~5ｖｏｌ％添加した場合、
２５…無添加の場合、２６…２−アミノエタノールを６
×１０~5ｖｏｌ％添加した場合、２７…２−アミノエタ
ノールを６×１０~3ｖｏｌ％添加した場合、２８…無添
加の場合、２９…非イオン界面活性剤１０~7ｍｏｌ／ｌ
とｍ−アミノフェノールを１ｖｏｌ％添加した場合、３
０…無添加の場合、３１…非イオン界面活性剤１０~7ｍ
ｏｌ／ｌとホルムアミドを０．５ｖｏｌ％添加した場
合、３２…無添加の場合、３３…非イオン界面活性剤１
０~7ｍｏｌ／ｌとベンジルアミンを１０~5ｍｏｌ／ｌ添
加した場合、３４…超純水製造部、３５…ゼータ電位制
御物質貯蔵部、３６…混合量調節器、３７…洗浄槽、３
８…Ｓｉウエハ搬送系。1 ... Substrate, 2 ... Fine particles, 3 ... Surface charge, 4 ... Bare Si particles, 5 ... Si particles, 6 ... Polystyrene particles, 7 ... Sliding surface, 8 ... 4 inch Si wafer, 9 ... Liquid tank, 10 ... No addition In the case of, 11 ... 2-aminoethanol is added at 6 × 10 to 5 vo
When 1% is added, 12 ... Ethanol is added by 1 vol%, 13 ... Hydrochloric acid is added, 14 ... 2-Aminoethanol is added by 6 × 10 to 5 vol%, 15
... when hydrochloric acid is added, 16 ... when 2-aminoethanol is added at 6x10 to 5 vol%, 17 ... when not added, and 18 ... nonionic surfactant 10 to 6 mol / l and 2-
When 6 × 10 to 5 vol% of amino ethanol is added,
19 ... In the case of no addition, 20 ... Nonionic surfactant 10 to 6
mol / l and 2-aminoethanol the 6 × 10 ~ 5 vol
%, 21 ... No addition, 22 ... Nonionic surfactant 10 to 6 mol / l and 2-aminoethanol 6 × 10 to 5 vol%, 23 ... No addition, 24 ... and a non-ionic surfactant 10 ~ 6 mol / l 2-
When 6 × 10 to 5 vol% of amino ethanol is added,
25 ... In case of no addition, 26 ... 2-aminoethanol 6
When 10 × 5 to 5 vol% is added, 27 ... 2-Aminoethanol is added at 6 × 10 to 3 vol%, 28 ... When it is not added, 29 ... Nonionic surfactant 10 to 7 mol / l
When adding 1 vol% of m-aminophenol and 3
0 ... In case of no addition, 31 ... Nonionic surfactant 10 to 7 m
If 0.5 vol% of ol / l and formamide are added, 32 ... Without addition, 33 ... Nonionic surfactant 1
When 0 to 7 mol / l and benzylamine are added to 10 to 5 mol / l, 34 ... Ultrapure water producing section, 35 ... Zeta potential control substance storage section, 36 ... Mixing amount controller, 37 ... Washing tank, 3
8 ... Si wafer transfer system.
フロントページの続き (72)発明者 岡 齊 横浜市戸塚区吉田町292番地株式会社日立 製作所生産技術研究所内Front Page Continuation (72) Inventor, Osamu Oka, 292 Yoshida-cho, Totsuka-ku, Yokohama City, Hitachi, Ltd.
Claims (14)
位）を制御できる物質を、該溶液中に１０~7〜２５ｖｏ
ｌ％の範囲の添加濃度で添加することにより、溶液中に
ある被吸着体である前記微粒子の付着を防止あるいは低
減することを特徴とする液中微粒子付着制御法。1. A substance capable of controlling the zeta potential (surface potential) of fine particles in a solution is added to the solution in an amount of 10 to 7 to 25 vo.
A method for controlling adhesion of fine particles in a liquid, which comprises preventing or reducing the adhesion of the fine particles, which are the adsorbents, in a solution, by adding at an addition concentration in the range of 1%.
きる物質が、分子内に電荷分布のある物質（双極子モー
メントを持つ物質）である請求項１記載の液中微粒子付
着制御法。2. The method for controlling adhesion of fine particles in liquid according to claim 1, wherein the substance capable of controlling the zeta potential of the fine particles in the solution is a substance having a charge distribution in the molecule (a substance having a dipole moment).
きる物質が、１分子中に親水性の基と疎水性の基を持つ
物質である請求項１記載の液中微粒子付着制御法。3. The method for controlling adhesion of fine particles in a liquid according to claim 1, wherein the substance capable of controlling the zeta potential of the fine particles in the solution is a substance having a hydrophilic group and a hydrophobic group in one molecule.
きる物質が、分子末端から２〜６個目の原子のいずれ
か、あるいは複数個の原子の電荷分布が負である分子か
らなる物質である請求項１記載の液中微粒子付着制御
法。4. A substance capable of controlling the zeta potential of fine particles in a solution is a substance consisting of a molecule having any of the atoms 2 to 6 from the terminal of the molecule or a plurality of atoms having a negative charge distribution. A method for controlling adhesion of fine particles in a liquid according to claim 1.
きる物質が、イオン解離しにくい物質である請求項１記
載の液中微粒子付着制御法。5. The method for controlling adhesion of fine particles in liquid according to claim 1, wherein the substance capable of controlling the zeta potential of the fine particles in the solution is a substance which is less likely to undergo ion dissociation.
物質が、該疎水性の基の水素原子の一部あるいは全てを
ハロゲン原子で置き換えた物質である請求項３記載の液
中微粒子付着制御法。6. The substance according to claim 3, wherein the substance having a hydrophilic group and a hydrophobic group in one molecule is a substance in which a part or all of hydrogen atoms of the hydrophobic group are replaced with halogen atoms. Liquid particle adhesion control method.
きる物質が、１分子中にアミノ基と水酸基を有する物質
である請求項１記載の液中微粒子付着制御法。7. The method for controlling adhesion of fine particles in a liquid according to claim 1, wherein the substance capable of controlling the zeta potential of the fine particles in the solution is a substance having an amino group and a hydroxyl group in one molecule.
きる物質が、１分子中にアミド基を有する物質である請
求項１記載の液中微粒子付着制御法。8. The method for controlling adhesion of fine particles in a liquid according to claim 1, wherein the substance capable of controlling the zeta potential of the fine particles in the solution is a substance having an amide group in one molecule.
きる物質が、１分子中にベンゼン環とアミノ基を有する
物質である請求項１記載の液中微粒子付着制御法。9. The method for controlling adhesion of fine particles in a liquid according to claim 1, wherein the substance capable of controlling the zeta potential of the fine particles in the solution is a substance having a benzene ring and an amino group in one molecule.
つ物質が、該疎水性の基の水素原子の一部あるいは全て
をチッ素原子で置き換えた物質である請求項３記載の液
中微粒子付着制御法。10. The substance having a hydrophilic group and a hydrophobic group in one molecule is a substance in which a part or all of hydrogen atoms of the hydrophobic group are replaced with nitrogen atoms. Method for controlling adhesion of fine particles in liquid.
することにより行なう請求項２〜１０記載の液中微粒子
付着制御法。11. The method for controlling adhesion of fine particles in a liquid according to claim 2, which is carried out by adding two or more kinds of substances having different molecular lengths.
類以上の１分子中に親水性の基と疎水性の基を持つ物質
を添加することにより行なう請求項１記載の液中微粒子
付着制御法。12. Adhesion of fine particles in liquid according to claim 1, which is carried out by adding at least one nonionic surfactant and at least one substance having a hydrophilic group and a hydrophobic group in one molecule. Control method.
素水の混合液を含む酸性溶液またはアンモニア水と過酸
化水素水の混合液を含むアルカリ性溶液または超純水を
含む中性溶液である請求項１〜１３記載の液中微粒子付
着制御法。13. The solution is an acidic solution containing a mixed solution of hydrofluoric acid, hydrochloric acid and hydrogen peroxide solution, an alkaline solution containing a mixed solution of ammonia water and hydrogen peroxide solution, or a neutral solution containing ultrapure water. The method for controlling adhesion of fine particles in liquid according to claims 1 to 13.
スを含む無機物または有機物を含む化合物である請求項
１〜１４記載の液中微粒子付着制御法。14. The method for controlling adhesion of fine particles in liquid according to claim 1, wherein the adsorbent is a compound containing an inorganic substance or an organic substance including various metals, alloys, and ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3200252A JP2524020B2 (en) | 1990-08-20 | 1991-08-09 | Liquid particle adhesion control method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21971090 | 1990-08-20 | ||
| JP2-219710 | 1990-08-20 | ||
| JP3200252A JP2524020B2 (en) | 1990-08-20 | 1991-08-09 | Liquid particle adhesion control method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05138142A true JPH05138142A (en) | 1993-06-01 |
| JP2524020B2 JP2524020B2 (en) | 1996-08-14 |
Family
ID=26512050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3200252A Expired - Fee Related JP2524020B2 (en) | 1990-08-20 | 1991-08-09 | Liquid particle adhesion control method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2524020B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020642A1 (en) * | 1994-01-26 | 1995-08-03 | Daikin Industries, Ltd. | Cleaning agent and method |
| WO1998001897A1 (en) * | 1996-07-08 | 1998-01-15 | Matsushita Electric Industrial Co., Ltd. | Method of cleaning semiconductor device |
| JP2003221600A (en) * | 2001-11-16 | 2003-08-08 | Mitsubishi Chemicals Corp | Substrate surface-cleaning solution and method of cleaning the same |
| KR100471742B1 (en) * | 1995-09-07 | 2005-09-08 | 가부시끼가이샤 히다치 세이사꾸쇼 | Cleaning method and manufacturing method of semiconductor device using the same |
| KR100795622B1 (en) * | 2005-03-30 | 2008-01-17 | 다이닛뽕스크린 세이조오 가부시키가이샤 | Substrate treatment apparatus and substrate treatment method |
| US7704939B2 (en) | 2004-08-31 | 2010-04-27 | Sanyo Chemical Industries, Ltd. | Surfactant |
| US8324143B2 (en) | 2008-12-19 | 2012-12-04 | Sanyo Chemical Industries, Ltd. | Cleaning agent for electronic materials |
| JP2017033991A (en) * | 2015-07-29 | 2017-02-09 | 東京エレクトロン株式会社 | Liquid processing method and liquid processing apparatus |
| WO2020021733A1 (en) * | 2018-07-26 | 2020-01-30 | 日立化成株式会社 | Slurry, screening method, and polishing method |
-
1991
- 1991-08-09 JP JP3200252A patent/JP2524020B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995020642A1 (en) * | 1994-01-26 | 1995-08-03 | Daikin Industries, Ltd. | Cleaning agent and method |
| KR100471742B1 (en) * | 1995-09-07 | 2005-09-08 | 가부시끼가이샤 히다치 세이사꾸쇼 | Cleaning method and manufacturing method of semiconductor device using the same |
| WO1998001897A1 (en) * | 1996-07-08 | 1998-01-15 | Matsushita Electric Industrial Co., Ltd. | Method of cleaning semiconductor device |
| US6273959B1 (en) | 1996-07-08 | 2001-08-14 | Matsushita Electric Industrial Co., Ltd. | Method of cleaning semiconductor device |
| JP2003221600A (en) * | 2001-11-16 | 2003-08-08 | Mitsubishi Chemicals Corp | Substrate surface-cleaning solution and method of cleaning the same |
| US7704939B2 (en) | 2004-08-31 | 2010-04-27 | Sanyo Chemical Industries, Ltd. | Surfactant |
| KR100795622B1 (en) * | 2005-03-30 | 2008-01-17 | 다이닛뽕스크린 세이조오 가부시키가이샤 | Substrate treatment apparatus and substrate treatment method |
| US8324143B2 (en) | 2008-12-19 | 2012-12-04 | Sanyo Chemical Industries, Ltd. | Cleaning agent for electronic materials |
| JP2017033991A (en) * | 2015-07-29 | 2017-02-09 | 東京エレクトロン株式会社 | Liquid processing method and liquid processing apparatus |
| WO2020021733A1 (en) * | 2018-07-26 | 2020-01-30 | 日立化成株式会社 | Slurry, screening method, and polishing method |
| WO2020021729A1 (en) * | 2018-07-26 | 2020-01-30 | 日立化成株式会社 | Slurry and polishing method |
| JPWO2020021729A1 (en) * | 2018-07-26 | 2021-08-05 | 昭和電工マテリアルズ株式会社 | Slurry and polishing method |
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| Publication number | Publication date |
|---|---|
| JP2524020B2 (en) | 1996-08-14 |
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