JPH085655B2 - Cleaning method for polycrystalline silicon - Google Patents
Cleaning method for polycrystalline siliconInfo
- Publication number
- JPH085655B2 JPH085655B2 JP18033991A JP18033991A JPH085655B2 JP H085655 B2 JPH085655 B2 JP H085655B2 JP 18033991 A JP18033991 A JP 18033991A JP 18033991 A JP18033991 A JP 18033991A JP H085655 B2 JPH085655 B2 JP H085655B2
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- Prior art keywords
- polycrystalline silicon
- cleaning
- mixed solution
- weight
- water
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- Crystals, And After-Treatments Of Crystals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、チョクラルスキー半導
体シリコン単結晶引き上げ法の前処理工程としての多結
晶シリコン表面を洗浄する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning the surface of polycrystalline silicon as a pretreatment step of the Czochralski semiconductor silicon single crystal pulling method.
【０００２】[0002]
【従来の技術】従来、単結晶シリコンの製造方法にはチ
ョクラルスキー法（ＣＺ法）やフローティングゾーン法
（ＦＺ法）が知られているが、チョクラルスキー法は多
結晶シリコンを溶融し、種結晶である単結晶シリコンを
この多結晶シリコンの溶融液に接触した後ある速度で引
き上げて結晶成長させるものである。2. Description of the Related Art Conventionally, the Czochralski method (CZ method) and the floating zone method (FZ method) are known as methods for producing single crystal silicon, but the Czochralski method involves melting polycrystalline silicon, Single crystal silicon, which is a seed crystal, is brought into contact with the melt of the polycrystalline silicon and then pulled at a certain speed to grow crystals.
【０００３】ところが多結晶シリコンは、その表面が酸
化されていたり、また不純物等が付着しているため、通
常は溶融前に洗浄する。その洗浄方法としては、塩酸
と過酸化水素の混合溶液およびアンモニア水と過酸化水
素の混合溶液で洗浄する方法（ＲＣＡ洗浄）、フッ化
水素酸と硝酸の混合溶液（フッ硝酸）にて洗浄する方法
がある。However, since the surface of polycrystalline silicon is oxidized or impurities are attached, it is usually washed before melting. As the cleaning method, a method of cleaning with a mixed solution of hydrochloric acid and hydrogen peroxide and a mixed solution of ammonia water and hydrogen peroxide (RCA cleaning) and a mixed solution of hydrofluoric acid and nitric acid (fluorine nitric acid) are used. There is a way.
【０００４】[0004]
【発明が解決しようとする課題】ところが、の方法で
は、Ｎａ、Ｃｕ、Ｆｅ等の金属の不純物や有機物を除去
することができるがＳｉＯ2 の除去は完全には行なえな
い。しかも、５０℃以上に加温しないと除去効果が低く
７０℃以上になると過酸化水素あるいはアンモニア水の
急速な分解が起こり洗浄液を頻繁に交換する必要が生じ
る。However, according to the method (1), impurities such as Na, Cu, and Fe and organic substances can be removed, but SiO 2 cannot be completely removed. Moreover, the removal effect is low unless the temperature is raised to 50 ° C. or higher, and the hydrogen peroxide or ammonia water is rapidly decomposed at 70 ° C. or higher, which necessitates frequent replacement of the cleaning liquid.
【０００５】また、の方法では、（ａ）洗浄液の劣化
が激しいため、洗浄液の交換を頻繁に行わなければばら
ず、生産性が低い。（ｂ）洗浄液の温度が上昇するため
冷却を必要とするが特に処理量が多い場合には温度コン
トロールが困難である。（ｃ）表面のＳｉＯ2 だけでな
く多結晶シリコンまで溶解するので重量ロスが多い。
（ｄ）排水、排気中のＮＯｘを処理する手間を必要とす
る。（ｅ）フッ硝酸で洗浄した多結晶シリコンの表面
は、新たに酸化膜を作り易く、また不純物を取り込み易
いため移槽時間を短くする必要があった。In the method (a), since the cleaning liquid (a) is severely deteriorated, the cleaning liquid has to be replaced frequently, resulting in low productivity. (B) Cooling is required because the temperature of the cleaning liquid rises, but it is difficult to control the temperature particularly when the processing amount is large. (C) Since not only SiO 2 on the surface but also polycrystalline silicon is dissolved, there is a large weight loss.
(D) It takes time and effort to treat NOx in waste water and exhaust gas. (E) Since it is easy to newly form an oxide film on the surface of polycrystalline silicon washed with hydrofluoric nitric acid and impurities are easily taken in, it is necessary to shorten the transfer time.
【０００６】本発明は上記の点を解決しようとするもの
で、その目的は洗浄液の劣化が極めて少なく、しかも変
色がなく、かつ温度コントロールが容易に行なえ、多結
晶シリコンのロスが少ないにもかかわらずシリコン酸化
膜や不純物を容易に除去することができる多結晶シリコ
ンの洗浄方法を提供することにある。The present invention is intended to solve the above-mentioned problems, and the object thereof is that deterioration of the cleaning liquid is extremely small, there is no discoloration, the temperature is easily controlled, and the loss of polycrystalline silicon is small. Another object of the present invention is to provide a method for cleaning polycrystalline silicon that can easily remove a silicon oxide film and impurities.
【０００７】[0007]
【発明が解決しようとする課題】本発明の多結晶シリコ
ンの洗浄方法は、チョクラルスキー単結晶引き上げ法の
前工程として多結晶シリコンをフッ化水素酸、過酸化水
素および水の混合溶液で洗浄することを特徴とする。The method of cleaning polycrystalline silicon according to the present invention is a method of cleaning polycrystalline silicon with a mixed solution of hydrofluoric acid, hydrogen peroxide and water as a step before the Czochralski single crystal pulling method. It is characterized by doing.
【０００８】次に本発明を詳細に説明する。本発明は、
フッ化水素酸、過酸化水素および水の混合溶液にて洗浄
し、多結晶シリコンの表面の酸化膜や不純物を除去する
ものである。本発明において、チョクラルスキー法で単
結晶を製造する前に予め多結晶シリコンを洗浄するのに
用いる混合溶液の濃度としては、濃度５０重量％フッ化
水素酸水溶液１に対して濃度３１重量％過酸化水素水
０．０３〜４、水１〜１０の容量比で混合したものまた
は各成分がこの混合溶液の重量比であるフッ化水素、過
酸化水素、水の混合溶液が好ましいが、濃度５０重量％
フッ化水素酸水溶液１に対して濃度３１重量％過酸化水
素水０．３、水５近辺の容積比に相当する濃度が特に好
ましく、この濃度において、不純物やシリコン酸化膜を
完全に除去することができる。また、この混合溶液は内
部の多結晶シリコンまでエッチングすることはない。Next, the present invention will be described in detail. The present invention
Cleaning is performed with a mixed solution of hydrofluoric acid, hydrogen peroxide and water to remove the oxide film and impurities on the surface of the polycrystalline silicon. In the present invention, the concentration of the mixed solution used to wash the polycrystalline silicon in advance before producing a single crystal by the Czochralski method is such that the concentration is 31 wt% with respect to 50 wt% aqueous solution of hydrofluoric acid. A mixture of hydrogen peroxide water 0.03 to 4 and water 1 to 10 by volume or a mixed solution of hydrogen fluoride, hydrogen peroxide and water in which each component is the weight ratio of this mixed solution is preferable, but the concentration 50% by weight
A concentration corresponding to a volume ratio of hydrogen peroxide solution of 0.3% by weight to 0.3% of hydrofluoric acid aqueous solution 1 and water 5 is particularly preferable. At this concentration, impurities and silicon oxide film should be completely removed. You can Further, this mixed solution does not etch the polycrystalline silicon inside.
【０００９】なお、本発明において多結晶シリコンの表
面の洗浄に用いられる混合溶液の各成分の濃度は、濃度
５０重量％フッ化水素酸と濃度３１重量％過酸化水素水
との容積比で表してあるが、これはあくまでも最終的に
洗浄に用いられる溶液の各成分がここで定義する容積比
で混合したものと同一の組成になっていればよいのであ
って、混合する際に必ず濃度５０重量％フッ化水素酸と
濃度３１重量％過酸化水素水を用いることを意味するも
のではなく、上記と異なる濃度の各成分を混合したもの
であってもよいことはいうまでもない。ただし、濃度５
０重量％近辺の濃度のフッ化水素酸や濃度３１重量％近
辺の濃度の過酸化水素水は市販されているため、ここで
述べた混合比率と同一かあるいはほぼ近い比率で混合し
使用するのに都合がよい。The concentration of each component of the mixed solution used for cleaning the surface of polycrystalline silicon in the present invention is expressed by the volume ratio of 50 wt% hydrofluoric acid and 31 wt% hydrogen peroxide solution. However, it is only necessary that each component of the solution finally used for cleaning has the same composition as that mixed in the volume ratio defined here, and the concentration of 50% is always required when mixing. It goes without saying that it does not mean that the weight% hydrofluoric acid and the hydrogen peroxide solution having a concentration of 31% by weight are used, and that each component having a concentration different from the above may be mixed. However, concentration 5
Since hydrofluoric acid having a concentration of about 0% by weight and hydrogen peroxide solution having a concentration of about 31% by weight are commercially available, they should be used by mixing them at the same or nearly the same mixing ratio as described here. It is convenient for.
【００１０】また、本発明の洗浄方法においては、洗浄
の際に激しい反応は起こらず、温度上昇はなく、従って
温度コントロールが容易である。混合溶液の温度は３５
℃以上であることが好ましく、これにより不純物や酸化
シリコンの除去効果が向上する。Further, in the cleaning method of the present invention, a vigorous reaction does not occur during cleaning, the temperature does not rise, and therefore the temperature control is easy. The temperature of the mixed solution is 35
It is preferable that the temperature is not lower than 0 ° C., which improves the effect of removing impurities and silicon oxide.
【００１１】また、本発明の洗浄方法においては、ま
ず、フッ化水素酸、過酸化水素および水の混合溶液に多
結晶シリコンを浸漬する。洗浄時間としては１〜１０分
が好ましい。その後、純水槽に浸漬して水洗後乾燥す
る。In the cleaning method of the present invention, first, polycrystalline silicon is immersed in a mixed solution of hydrofluoric acid, hydrogen peroxide and water. The washing time is preferably 1 to 10 minutes. Then, it is immersed in a pure water tank, washed with water and dried.
【００１２】また、本発明の洗浄方法においては、２段
階以上の洗浄でも良く、この場合全ての洗浄がフッ化水
素酸、過酸化水素および水の混合溶液による洗浄である
必要はない。Further, in the cleaning method of the present invention, the cleaning may be carried out in two or more steps, and in this case, all cleaning need not be cleaning with a mixed solution of hydrofluoric acid, hydrogen peroxide and water.
【００１３】本発明によれば、多結晶シリコン塊の表面
のシリコン酸化膜や不純物が極限にまで洗浄除去され
る。具体的には、Ｆｅ，Ｃｕ，Ｎｉ，Ｃｒにつき下記の
不純物濃度となるまで洗浄精製が可能である。 Ｆｅ： ０．５ 重量ｐｐｂ以下 Ｃｕ： ０．０５重量ｐｐｂ以下 Ｎｉ： ０．０５重量ｐｐｂ以下 Ｃｒ： ０．２ 重量ｐｐｂ以下 なお、上記不純物濃度は、多結晶シリコン表面の不純物
重量を多結晶シリコン重量で割った値である。According to the present invention, the silicon oxide film and impurities on the surface of the polycrystalline silicon block are cleaned and removed to the utmost limit. Specifically, Fe, Cu, Ni, and Cr can be washed and purified to the following impurity concentrations. Fe: 0.5 weight ppb or less Cu: 0.05 weight ppb or less Ni: 0.05 weight ppb or less Cr: 0.2 weight ppb or less The above impurity concentration is the weight of impurities on the surface of polycrystalline silicon. It is the value divided by the weight.
【００１４】本発明の洗浄方法においては、従来のよう
に硝酸を使用しないためＮＯｘの発生がなく、そのため
ＮＯｘの処理を必要とせず安全に行なうことができる。In the cleaning method of the present invention, since nitric acid is not used as in the conventional case, NOx is not generated, and therefore, NOx treatment is not required and can be safely performed.
【００１５】また、フッ化水素酸、過酸化水素および水
の混合液のため、フッ硝酸と比較して洗浄液のコストが
安価である。Further, since the mixed solution of hydrofluoric acid, hydrogen peroxide and water is used, the cost of the cleaning solution is lower than that of hydrofluoric nitric acid.
【００１６】さらに、表面のシリコン酸化膜や不純物の
みを除去し、その内部の多結晶シリコンのエッチングま
では行なわれないため重量ロスがなく、多結晶シリコン
がエッチングされた時のような活性面が生じないため、
新たにその表面に酸化膜を生じることもない。Further, since only the silicon oxide film and impurities on the surface are removed and the polycrystalline silicon inside is not etched, there is no weight loss, and the active surface as when the polycrystalline silicon is etched does not occur. Because it does not occur,
No new oxide film is formed on the surface.
【００１７】さらに洗浄液の温度上昇がないため冷却設
備を必要とせず、温度コントロールを容易に行なうこと
ができる。Further, since the temperature of the cleaning liquid does not rise, cooling equipment is not required and the temperature can be easily controlled.
【００１８】また、ＮＯｘの発生や多結晶シリコンのエ
ッチング等による洗浄液の劣化がほとんどないため、単
位洗浄液当りの多結晶シリコンの処理量はフッ硝酸に比
べ多く、コスト安となるばかりか環境を害することもな
い。また、洗浄液の変色も見られない。Further, since the cleaning liquid is hardly deteriorated due to the generation of NOx and the etching of the polycrystalline silicon, the processing amount of the polycrystalline silicon per cleaning liquid is larger than that of hydrofluoric nitric acid, which not only lowers the cost but also harms the environment. Nothing. Moreover, discoloration of the cleaning liquid is not observed.
【００１９】以上のように不純物やシリコン酸化膜を除
去された多結晶シリコンは非常に高純度にまで高いレベ
ルの洗浄精製が行なわれているため、溶融されてチョク
ラルスキー法による超高純度の単結晶シリコンの製造に
使用するのに最適である。As described above, the polycrystalline silicon from which the impurities and the silicon oxide film have been removed has been subjected to a high level of cleaning and purification to a very high degree of purity, so that it is melted to obtain an ultrahigh purity by the Czochralski method. Best suited for use in the production of single crystal silicon.
【００２０】[0020]
【実施例】次に本発明を実施例および比較例を挙げて説
明する。 実施例１ 濃度５０重量％フッ化水素酸１．６リットル、濃度３１
重量％過酸化水素水０．５リットル、水８．０リットル
の混合溶液の温度を各々２５℃、３５℃、４０℃、５０
℃、６５℃、７３℃とし、この混合溶液に多結晶シリコ
ン１ｋｇを６分間浸漬して洗浄後、２５℃の水槽に４分
間浸漬して超音波水洗し、その後２５℃の水槽に４分間
浸漬して再度水洗し、その後２５℃の水槽に４分間浸漬
して最後の超音波水洗を行ない、最後にイソプロピルア
ルコールに４分間浸漬して乾燥させた。EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples. Example 1 Concentration of 50 wt% hydrofluoric acid 1.6 liters, concentration 31
The temperature of a mixed solution of 0.5% by weight hydrogen peroxide water and 8.0 liters of water is 25 ° C, 35 ° C, 40 ° C and 50 ° C, respectively.
C., 65.degree. C., 73.degree. C., 1 kg of polycrystalline silicon is soaked in this mixed solution for 6 minutes for cleaning, then immersed in a 25.degree. C. water tank for 4 minutes and ultrasonically washed, and then immersed in a 25.degree. C. water tank for 4 minutes. Then, it was again washed with water, then immersed in a water bath at 25 ° C. for 4 minutes for the final ultrasonic water washing, and finally immersed in isopropyl alcohol for 4 minutes to be dried.
【００２１】この洗浄された多結晶シリコンの表面のＦ
ｅ、Ｃｕ、Ｎｉ、Ｃｒの濃度を分析し、洗浄液の温度と
の関係を図１〜図４に示す。F on the surface of the washed polycrystalline silicon
The concentrations of e, Cu, Ni, and Cr were analyzed, and the relationship with the temperature of the cleaning liquid is shown in FIGS.
【００２２】なお、多結晶シリコンの表面不純物濃度の
分析は、次のような原子吸光法にて定量した。濃度５０
重量％のフッ化水素酸水溶液１５０ミリリットル、濃度
３１重量％の過酸化水素水３ミリリットル、水１５０ミ
リリットルの混合溶液を８０℃に加湿し、これに多結晶
シリコン３００ｇを１０分間浸漬する。その後多結晶シ
リコンを１０ミリリットルの水ですすいだ後、これらの
溶液を蒸発乾固させ、１０％硝酸水溶液３０ミリリット
ルを加えて定量分析を行なう。The analysis of the surface impurity concentration of the polycrystalline silicon was carried out by the following atomic absorption method. Concentration 50
A mixed solution of 150 ml of a wt% hydrofluoric acid aqueous solution, 3 ml of a hydrogen peroxide solution having a concentration of 31 wt% and 150 ml of water is humidified at 80 ° C., and 300 g of polycrystalline silicon is immersed in this for 10 minutes. After rinsing the polycrystalline silicon with 10 ml of water, these solutions are evaporated to dryness, and 30 ml of 10% nitric acid aqueous solution is added for quantitative analysis.
【００２３】図１〜図４より、洗浄液の温度が高い程多
結晶シリコンの表面の不純物濃度が低く、特に３５℃以
上の洗浄液温度ではその傾向が顕著である。1 to 4, the higher the temperature of the cleaning liquid, the lower the impurity concentration on the surface of the polycrystalline silicon, and this tendency is remarkable at the cleaning liquid temperature of 35 ° C. or higher.
【００２４】実施例２ 濃度５０重量％フッ化水素酸１．６リットル、濃度３１
重量％過酸化水素水０．５リットル、水８．０リットル
の混合溶液を４５℃まで加温し、この混合溶液に多結晶
シリコン１ｋｇを４分間浸漬して洗浄後、２５℃の水槽
に４分間浸漬して超音波水洗した。その後前工程の混合
溶液と同組成で同量の別の混合溶液に４分間浸漬して洗
浄した。その後実施例１と同様の方法で水洗、乾燥し
た。Example 2 Concentration 50 wt% hydrofluoric acid 1.6 liters, concentration 31
A mixed solution of 0.5% by weight hydrogen peroxide water and 8.0 liter of water is heated to 45 ° C., 1 kg of polycrystalline silicon is dipped in this mixed solution for 4 minutes for cleaning, and then placed in a 25 ° C. water tank. It was immersed for a minute and washed with ultrasonic water. Then, it was immersed in another mixed solution of the same composition and the same amount as the mixed solution of the previous step for 4 minutes for cleaning. Then, it was washed with water and dried in the same manner as in Example 1.
【００２５】同じ洗浄液を繰り返して使用して多結晶シ
リコンを洗浄した。被洗浄物表面のの不純物（Ｆｅ、Ｃ
ｕ）濃度と洗浄処理量の関係を調べ、その結果を図５、
図６に示す。The same cleaning solution was repeatedly used to clean the polycrystalline silicon. Impurities on the surface of the object to be cleaned (Fe, C
u) The relationship between the concentration and the amount of cleaning treatment was investigated, and the result is shown in FIG.
As shown in FIG.
【００２６】図５、図６より洗浄液を繰り返して使用し
てもＦｅ、Ｃｕの不純物濃度があまり変化せず、従って
洗浄液の劣化が非常に少ないことがわかる。また、被洗
浄表面の不純物濃度はＮｉについても０．００８ｐｐｂ
〜０．０１ｐｐｂ、また、Ｃｒについても０．０５ｐｐ
ｂ〜０．１ｐｐｂで、洗浄液の繰返し使用による劣化の
非常に少ないことを確認している。It can be seen from FIGS. 5 and 6 that the impurity concentrations of Fe and Cu do not change much even if the cleaning liquid is repeatedly used, and therefore the deterioration of the cleaning liquid is very small. The impurity concentration of the surface to be cleaned is 0.008 ppb for Ni.
~ 0.01 ppb, and 0.05 pp for Cr
From b to 0.1 ppb, it has been confirmed that there is very little deterioration due to repeated use of the cleaning liquid.
【００２７】[0027]
【発明の効果】以上の説明で明らかな様に本発明の多結
晶シリコンの洗浄方法によれば、洗浄液の劣化や変色が
ないため洗浄液を頻繁にかえる必要がなく、また温度コ
ントロールが容易に行なえ、生産性が高く安全に多結晶
シリコンの表面酸化膜や不純物を除去することができ
る。As is clear from the above description, according to the method for cleaning polycrystalline silicon of the present invention, there is no deterioration or discoloration of the cleaning liquid, so that it is not necessary to change the cleaning liquid frequently, and the temperature can be easily controlled. Highly productive, the surface oxide film of polycrystalline silicon and impurities can be removed safely.
【図１】本発明の多結晶シリコンの洗浄方法による洗浄
後の多結晶シリコン表面のＦｅ不純物濃度と温度の関係
を示すグラフである。FIG. 1 is a graph showing the relationship between the Fe impurity concentration on the surface of polycrystalline silicon and the temperature after cleaning by the method for cleaning polycrystalline silicon according to the present invention.
【図２】本発明の多結晶シリコンの洗浄方法による洗浄
後の多結晶シリコン表面のＣｕ不純物濃度と温度の関係
を示すグラフである。FIG. 2 is a graph showing the relationship between the Cu impurity concentration on the surface of polycrystalline silicon and the temperature after cleaning by the method for cleaning polycrystalline silicon according to the present invention.
【図３】本発明の多結晶シリコンの洗浄方法による洗浄
後の多結晶シリコン表面のＮｉ不純物濃度と温度の関係
を示すグラフである。FIG. 3 is a graph showing the relationship between the Ni impurity concentration on the surface of polycrystalline silicon after cleaning and the temperature after cleaning by the method for cleaning polycrystalline silicon according to the present invention.
【図４】本発明の多結晶シリコンの洗浄方法による洗浄
後の多結晶シリコン表面のＣｒ不純物濃度と温度の関係
を示すグラフである。FIG. 4 is a graph showing the relationship between the Cr impurity concentration on the surface of polycrystalline silicon and the temperature after cleaning by the method for cleaning polycrystalline silicon according to the present invention.
【図５】本発明の多結晶シリコンの洗浄方法における洗
浄処理量と被洗浄物表面のＦｅ不純物濃度を示すグラフ
である。FIG. 5 is a graph showing the amount of cleaning treatment and the Fe impurity concentration on the surface of the object to be cleaned in the method for cleaning polycrystalline silicon according to the present invention.
【図６】本発明の多結晶シリコンの洗浄方法における洗
浄処理量と被洗浄物表面のＣｕ不純物濃度を示すグラフ
である。FIG. 6 is a graph showing the amount of cleaning treatment and the Cu impurity concentration on the surface of the object to be cleaned in the method for cleaning polycrystalline silicon according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浅子 喜一郎 群馬県安中市磯部２丁目13番１号 信越半 導体株式会社 半導体磯部研究所内 (72)発明者 清水 敬也 群馬県安中市磯部２丁目13番１号 信越半 導体株式会社 半導体磯部研究所内 (72)発明者 横田 修二 群馬県安中市磯部２丁目13番１号 信越半 導体株式会社 磯部工場内 (56)参考文献 特開 平５−33070（ＪＰ，Ａ) 特開 昭62−288109（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiichiro Asako 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Semiconductor Co., Ltd., Semiconductor Isobe Research Center (72) Inventor Keiya Shimizu 2 Isobe, Annaka-shi, Gunma Prefecture 1-chome 13-1 Shin-Etsu Semiconductor Co., Ltd., Semiconductor Isobe Research Laboratory (72) Inventor Shuji Yokota 2-1-13-1 Isobe, Annaka-shi, Gunma Shin-Etsu Semiconductor Co., Ltd. Isobe Factory (56) Reference JP 5 -33070 (JP, A) JP-A-62-288109 (JP, A)
Claims (3)
引き上げ法の前工程として高純度多結晶シリコンをフッ
化水素、過酸化水素および水の混合溶液で処理する多結
晶シリコンの洗浄方法であって、その混合溶液が濃度５
０重量％フッ化水素酸水溶液１に対して濃度３１重量％
過酸化水素水０．０３〜４、水１〜１０の容量比で混合
調整された混合溶液の当該各成分重量比と同一の混合溶
液であることを特徴とする多結晶シリコンの洗浄方法。1. A method of cleaning polycrystalline silicon, which comprises treating high-purity polycrystalline silicon with a mixed solution of hydrogen fluoride, hydrogen peroxide, and water as a pre-step of the Czochralski semiconductor silicon single crystal pulling method, Concentration of mixed solution is 5
Concentration 31% by weight to 0% by weight hydrofluoric acid aqueous solution 1
A method for cleaning polycrystalline silicon, which is a mixed solution having the same weight ratio of the respective components of the mixed solution prepared by mixing and adjusting the volume ratio of hydrogen peroxide water 0.03 to 4 and water 1 to 10.
上の混合溶液で処理することを特徴とする請求項１に記
載の多結晶シリコンの洗浄方法。2. The method for cleaning polycrystalline silicon according to claim 1, wherein in the method for cleaning polycrystalline silicon, treatment is performed with a mixed solution at 35 ° C. or higher.
物濃度が０．５重量ｐｐｂ以下であり、Ｃｕ，Ｎｉの各
不純物濃度が０．０５重量ｐｐｂ以下であり、Ｃｒ含有
量が０．２重量ｐｐｂ以下である請求項１に記載の多結
晶シリコンの洗浄方法。3. The Fe impurity concentration on the surface of the polycrystalline silicon after cleaning is 0.5 weight ppb or less, each impurity concentration of Cu and Ni is 0.05 weight ppb or less, and the Cr content is 0.2. The method for cleaning polycrystalline silicon according to claim 1, which has a weight of ppb or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18033991A JPH085655B2 (en) | 1991-06-25 | 1991-06-25 | Cleaning method for polycrystalline silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18033991A JPH085655B2 (en) | 1991-06-25 | 1991-06-25 | Cleaning method for polycrystalline silicon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH054811A JPH054811A (en) | 1993-01-14 |
| JPH085655B2 true JPH085655B2 (en) | 1996-01-24 |
Family
ID=16081497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18033991A Expired - Fee Related JPH085655B2 (en) | 1991-06-25 | 1991-06-25 | Cleaning method for polycrystalline silicon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085655B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2857042B2 (en) * | 1993-10-19 | 1999-02-10 | 新日本製鐵株式会社 | Cleaning liquid for silicon semiconductor and silicon oxide |
| US5753567A (en) * | 1995-08-28 | 1998-05-19 | Memc Electronic Materials, Inc. | Cleaning of metallic contaminants from the surface of polycrystalline silicon with a halogen gas or plasma |
| US5851303A (en) * | 1996-05-02 | 1998-12-22 | Hemlock Semiconductor Corporation | Method for removing metal surface contaminants from silicon |
| DE19741465A1 (en) | 1997-09-19 | 1999-03-25 | Wacker Chemie Gmbh | Polycrystalline silicon |
| JP4658453B2 (en) * | 2002-11-14 | 2011-03-23 | ヘムロック・セミコンダクター・コーポレーション | Flowable chip, method for producing and using the same, and apparatus used for carrying out the method |
| US7223303B2 (en) * | 2004-08-26 | 2007-05-29 | Mitsubishi Materials Corporation | Silicon cleaning method for semiconductor materials and polycrystalline silicon chunk |
| US7270706B2 (en) | 2004-10-04 | 2007-09-18 | Dow Corning Corporation | Roll crusher to produce high purity polycrystalline silicon chips |
| JP2007145676A (en) * | 2005-11-30 | 2007-06-14 | Toshiba Ceramics Co Ltd | Method for improving surface purity of lutetium silicate crystal |
| DE102006031105A1 (en) * | 2006-07-05 | 2008-01-10 | Wacker Chemie Ag | Process for the purification of polysilicon breakage |
| DE102007047210A1 (en) | 2007-10-02 | 2009-04-09 | Wacker Chemie Ag | Polycrystalline silicon and process for its preparation |
| US7905963B2 (en) | 2008-11-28 | 2011-03-15 | Mitsubishi Materials Corporation | Apparatus and method for washing polycrystalline silicon |
| JP5751748B2 (en) | 2009-09-16 | 2015-07-22 | 信越化学工業株式会社 | Polycrystalline silicon lump group and method for producing polycrystalline silicon lump group |
| CN105951184A (en) * | 2016-05-12 | 2016-09-21 | 华南师范大学 | Texturing method of diamond wire-cut polycrystalline silicon wafer |
| CN109841496A (en) * | 2017-11-27 | 2019-06-04 | 东莞新科技术研究开发有限公司 | The cleaning method of semi-conductor silicon chip |
-
1991
- 1991-06-25 JP JP18033991A patent/JPH085655B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH054811A (en) | 1993-01-14 |
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