JP2696290B2 - Method for measuring interstitial oxygen concentration in oxygen-precipitated silicon single crystal - Google Patents
Method for measuring interstitial oxygen concentration in oxygen-precipitated silicon single crystalInfo
- Publication number
- JP2696290B2 JP2696290B2 JP14487992A JP14487992A JP2696290B2 JP 2696290 B2 JP2696290 B2 JP 2696290B2 JP 14487992 A JP14487992 A JP 14487992A JP 14487992 A JP14487992 A JP 14487992A JP 2696290 B2 JP2696290 B2 JP 2696290B2
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- absorption
- single crystal
- peak
- silicon single
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 69
- 239000001301 oxygen Substances 0.000 title claims description 67
- 229910052760 oxygen Inorganic materials 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 53
- 239000013078 crystal Substances 0.000 title claims description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052710 silicon Inorganic materials 0.000 title claims description 32
- 239000010703 silicon Substances 0.000 title claims description 32
- 238000010521 absorption reaction Methods 0.000 claims description 54
- 238000005259 measurement Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009529 body temperature measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 101100001670 Emericella variicolor andE gene Proteins 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By Optical Means (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸素析出したシリコン
単結晶中の格子間酸素濃度を正確に測定し得る方法に関
する。The present invention relates to a method for accurately measuring the interstitial oxygen concentration in an oxygen-precipitated silicon single crystal.
【０００２】[0002]
【従来の技術】従来より、シリコン単結晶の引上げには
チョクラルスキー（ＣＺ）法が採用されており、該方法
ではシリコン溶融体を収容するルツボとして石英製のル
ツボが用いられるため、石英製のルツボからシリコン溶
融体中に酸素が溶解し、それがシリコン単結晶中に取り
込まれることが知られている。シリコン単結晶中に取り
込まれた酸素はシリコン単結晶中において格子間酸素と
して存在したり、酸素原子どうしが集まってクラスター
を形成して析出した状態で存在したりする。2. Description of the Related Art Conventionally, the Czochralski (CZ) method has been employed for pulling a silicon single crystal. In this method, a quartz crucible is used as a crucible for containing a silicon melt. It is known that oxygen is dissolved from a crucible into a silicon melt and is taken into a silicon single crystal. Oxygen taken into the silicon single crystal exists as interstitial oxygen in the silicon single crystal, or exists in a state where oxygen atoms gather to form clusters and precipitate.
【０００３】そして、シリコン単結晶中に存在する酸素
は、ある場合は素子としてのトランジスターの特性不良
を引き起こす欠陥の原因となり、他の場合はゲッター効
果を発現したりウェーハの機械的強度を増大させたりす
ることとなり、また、格子間酸素と析出酸素とはシリコ
ン単結晶に与える物性上の影響も異なるため、それぞれ
の酸素を明確に分離した形で正確に測定すること、特に
格子間酸素濃度を正確に測定することが必要とされてい
た。[0003] Oxygen present in a silicon single crystal sometimes causes a defect that causes a characteristic failure of a transistor as an element. In other cases, oxygen causes a getter effect or increases the mechanical strength of a wafer. In addition, interstitial oxygen and precipitated oxygen have different effects on the physical properties of the silicon single crystal.Therefore, it is necessary to accurately measure each oxygen in a clearly separated form. Accurate measurement was needed.
【０００４】従来は、このようなシリコン単結晶中の格
子間酸素濃度〔Ｏｉ〕を測定するために、格子間酸素の
逆対称伸縮赤外局在振動モードの吸収を利用した方法、
すなわち室温での１１０６ｃｍ-1吸収ピークのピーク高
さより定量する方法が最も基本的な方法として知られて
いる。そして、この方法を適用するに当り、ピーク高さ
を実測するためのスペクトルベースラインを１３００ｃ
ｍ-1〜９００ｃｍ-1間にひく方法（Ａ法〔T. Iizuka et
al., J. Electrochem. Soc., 132, 1707 (1985)〕）が
（社）日本電子工業振興協会（ＪＥＩＤＡ）の標準とし
てひろく用いられており、更に図２等で後述するよう
に、ベースラインを１１５０ｃｍ-1〜１０５０ｃｍ-1間
のようなより狭い波数範囲にひく方法（Ｂ法）も産業上
ひろく用いられている。Conventionally, in order to measure the interstitial oxygen concentration [Oi] in such a silicon single crystal, a method using the absorption of an antisymmetric stretching infrared localized vibration mode of interstitial oxygen,
That is, a method of quantification from the peak height of the 1106 cm -1 absorption peak at room temperature is known as the most basic method. In applying this method, a spectrum baseline for actually measuring the peak height is set to 1300c.
Method of drawing between m -1 and 900 cm -1 (Method A [T. Iizuka et al.
al., J. Electrochem. Soc., 132, 1707 (1985)]) has been widely used as a standard of the Japan Electronic Industry Development Association (JEIDA), and as described later in FIG. The method of drawing a line over a narrower wave number range such as between 1150 cm -1 and 1050 cm -1 (method B) is also widely used in industry.
【０００５】as-grownのＣＺ結晶や酸素析出物を含まな
いＣＺ結晶の場合には、上述のベースライン設定方法と
して、Ａ法を用いてもＢ法を用いても、得られる〔Ｏ
ｉ〕評価値に有意差を生ずるようなことがなく問題は起
こらない。しかし、過飽和状態にあるＣＺ−Ｓｉ結晶中
の酸素が熱処理プロセス中に結晶内析出物を形成した酸
素析出結晶の場合には、その赤外吸収スペクトルには結
晶内に溶解した格子間酸素の局在振動モードの吸収ピー
クの他に、酸素析出物による赤外吸収バンドが現れるよ
うになる。一般的な〔Ｏｉ〕評価には、格子間酸素吸収
ピークの中で最も強い吸収を示す１１０６ｃｍ-1の逆対
称伸縮振動モードを利用しているが、酸素析出結晶にお
いてはこれに重畳して１３００〜１０００ｃｍ-1付近に
酸素析出物による吸収バンドが現れている。In the case of an as-grown CZ crystal or a CZ crystal containing no oxygen precipitates, it can be obtained by using the method A or the method B as the above-mentioned baseline setting method [O
i) There is no significant difference in the evaluation value and no problem occurs. However, in the case of oxygen-precipitated crystals in which oxygen in the supersaturated CZ-Si crystal forms an intracrystalline precipitate during the heat treatment process, the infrared absorption spectrum shows localization of interstitial oxygen dissolved in the crystal. In addition to the absorption peak in the vibration mode, an infrared absorption band due to the oxygen precipitate appears. In general [Oi] evaluation, an antisymmetric stretching vibration mode of 1106 cm -1 showing the strongest absorption among the interstitial oxygen absorption peaks is used. An absorption band due to oxygen precipitates appears at about 1000 cm -1 .
【０００６】図２はこの状況を、初期酸素濃度１９ｐｐ
ｍａ（ＪＥＩＤＡ標準の〔Ｏｉ〕スケール）のas-grown
結晶に対して〔８００℃，４時間＋１０００℃，１７時
間〕の二段熱処理を施して、酸素析出量（Δ〔Ｏｉ〕）
を７ｐｐｍａとした酸素析出結晶（２ｍｍ厚）につい
て、実測スペクトルによって示したものである。この酸
素析出結晶では、１１２０ｃｍ-1と１２２０ｃｍ-1にピ
ークをもつブロードなダブレット状の酸素析出吸収バン
ドを示し、特に１１２０ｃｍ-1ピークの析出吸収バンド
は１１０６ｃｍ-1での格子間酸素（Ｏｉ）吸収ピークと
強く重なり合ってしまう。従って、Ｏｉの吸収量のみを
析出による吸収から分離して求めることは困難となる。
しかも、析出による吸収バンドのスペクトル形状は、
〔K. Tempelhoff and F. Spiegelberg, in "Semiconduc
tor Silicon 1977" (H. R. Huff andE. Sirtl, eds.),
pp. 585-595, Electrochem. Soc., Princeton, New Jer
sey,1977〕の文献にも報告されているように、酸素析出
熱処理の温度や時間が変わることによって大きく変化す
るため、室温測定での１１０６ｃｍ-1 Ｏｉ吸収と酸素
析出吸収を正しく分離することは不可能である。FIG. 2 shows this situation as an initial oxygen concentration of 19 pp.
ma (JEIDA standard [Oi] scale) as-grown
The crystal is subjected to a two-step heat treatment at [800 ° C., 4 hours + 1000 ° C., 17 hours], and the amount of precipitated oxygen (Δ [Oi])
Of the oxygen-precipitated crystal (thickness: 2 mm) having a concentration of 7 ppma. This oxygen-precipitated crystal exhibits a broad doublet-like oxygen-precipitation absorption band having peaks at 1120 cm -1 and 1220 cm -1 , and particularly, the precipitation-absorption band at 1120 cm -1 peak has an interstitial oxygen (Oi) at 1106 cm -1. It strongly overlaps with the absorption peak. Therefore, it is difficult to obtain only the absorption amount of Oi separately from the absorption due to precipitation.
Moreover, the spectral shape of the absorption band due to precipitation is
[K. Tempelhoff and F. Spiegelberg, in "Semiconduc
tor Silicon 1977 "(HR Huff andE. Sirtl, eds.),
pp. 585-595, Electrochem. Soc., Princeton, New Jer
As reported in the literature of Sey, 1977], since the temperature and time of the oxygen precipitation heat treatment change greatly, it is difficult to correctly separate the 1106 cm -1 Oi absorption and the oxygen precipitation absorption in room temperature measurement. Impossible.
【０００７】図２において、実際の格子間酸素Ｏｉに相
当する吸収量は図中のａ−ｂの長さでなければならない
が、一般にひろく知られているＡ法によるベースライン
を用いると、ａ−ｄの長さをＯｉ吸収量と見なしてしま
うため、実際よりもかなり（ｂ−ｄの長さ分）高目に
〔Ｏｉ〕を評価してしまう。Ｂ法によるベースラインを
用いた場合は、Ａ法の場合よりも改善されるが、ａ−ｃ
の長さをＯｉ吸収量と見なすため、やはりｂ−ｃの長さ
分だけ高目に〔Ｏｉ〕を評価してしまう。In FIG. 2, the absorption amount corresponding to the actual interstitial oxygen Oi must be the length of a-b in the figure, but if a baseline widely known by the method A is used, a Since the length of −d is regarded as the Oi absorption amount, [Oi] is evaluated to be considerably higher (by the length of b−d) than the actual. When the baseline obtained by the method B is used, the improvement is obtained as compared with the case of the method A.
Since the length of Oi is regarded as the Oi absorption amount, [Oi] is also evaluated higher by the length of bc.
【０００８】以上の説明で明らかなように、酸素析出結
晶の〔Ｏｉ〕測定では、Ａ法，Ｂ法いずれを用いたとし
ても析出酸素に基づく吸収バンドを含んだ形でしか、ピ
ーク高さを求めることができず、正確な測定値を得るこ
とは不可能である。すなわち、以下に示す低温赤外吸収
法により得られた〔Ｏｉ〕信頼値と上記Ａ法及びＢ法で
得られた〔Ｏｉ〕評価値とを比較すると、図３に示すよ
うにこれら両法の〔Ｏｉ〕評価値は、〔Ｏｉ〕信頼値か
ら高い側へ偏寄していることがわかる。As is apparent from the above description, in the [Oi] measurement of the oxygen precipitate crystal, the peak height is determined only in a form including the absorption band based on the precipitated oxygen, regardless of whether the method A or the method B is used. It cannot be determined and it is impossible to obtain accurate measurements. That is, comparing the [Oi] confidence value obtained by the low-temperature infrared absorption method shown below with the [Oi] evaluation value obtained by the above method A and method B, as shown in FIG. It can be seen that the [Oi] evaluation value deviates from the [Oi] reliability value to a higher side.
【０００９】酸素析出に影響されずに〔Ｏｉ〕の信頼値
を求めるためには、３．８Ｋという低温で１１３６ｃｍ
-1の格子間酸素ピークの赤外吸収測定を行い、酸素析出
吸収のブロードバンドと格子間酸素吸収のシャープなピ
ークを分離すればよい。この方法により得られた赤外吸
収スペクトルを図４に示す。図中の下部に斜線で示され
た部分は、酸素析出によるブロードな吸収バンドの一部
分を、１１８０〜１０８０ｃｍ-1の狭い波数範囲内で拡
大表示したものである。このブロードで変化の小さい吸
収バンド上に、格子間酸素（Ｏｉ）によるシャープな吸
収ピークが１１３６ｃｍ-1位置に現れるため、図中の破
線で示されるように、Ｏｉ吸収と酸素析出吸収とは、Ｏ
ｉピークのベースラインによって明瞭に分離することが
できる。このようにして３．８Ｋの低温測定により求め
られたＯｉの光吸収係数（酸素析出による吸収成分を含
まない）は、別に用意された酸素濃度標準Ｓｉ単結晶試
料を使って求められた３．８Ｋ測定の濃度検量線によ
り、格子間酸素濃度値に変換できる。この値は、酸素析
出による吸収成分を含まないので、酸素析出結晶中の
〔Ｏｉ〕の最も信頼性の高い値と考えられる。図３にお
ける横軸の〔Ｏｉ〕信頼値は、このようにして求められ
た〔Ｏｉ〕値である。In order to determine the reliability value of [Oi] without being affected by oxygen precipitation, 1136 cm at a low temperature of 3.8 K
An infrared absorption measurement of an interstitial oxygen peak of -1 may be performed to separate a broad band of oxygen precipitation absorption and a sharp peak of interstitial oxygen absorption. FIG. 4 shows the infrared absorption spectrum obtained by this method. The hatched portion in the lower part of the figure is an enlarged view of a part of a broad absorption band due to oxygen precipitation within a narrow wavenumber range of 1180 to 1080 cm -1 . Since a sharp absorption peak due to interstitial oxygen (Oi) appears at the position of 1136 cm -1 on the broad absorption band having a small change, as shown by the broken line in the figure, the Oi absorption and the oxygen precipitation absorption are: O
It can be clearly separated by the baseline of the i peak. The light absorption coefficient of Oi (excluding the absorption component due to oxygen precipitation) determined by the low-temperature measurement at 3.8 K in this manner was determined using a separately prepared oxygen concentration standard Si single crystal sample. It can be converted to an interstitial oxygen concentration value by a concentration calibration curve of 8K measurement. This value is considered to be the most reliable value of [Oi] in the oxygen-precipitated crystal since it does not include the absorption component due to oxygen precipitation. The [Oi] confidence value on the horizontal axis in FIG. 3 is the [Oi] value obtained in this manner.
【００１０】[0010]
【発明が解決しようとする課題】上記の低温赤外吸収法
を用いれば〔Ｏｉ〕信頼値を求めることが可能である
が、測定温度が非常に低いために、低温状態にするのが
困難であり、測定操作が非常に煩雑なものになり、多量
の試料について短時間に測定することが困難であり、ま
た、測定に要する機器が高価なものになってしまうとい
う問題があった。If the low-temperature infrared absorption method described above is used, the [Oi] reliability value can be obtained. However, since the measurement temperature is very low, it is difficult to make the temperature low. There is a problem that the measurement operation becomes very complicated, it is difficult to measure a large amount of sample in a short time, and the equipment required for the measurement becomes expensive.
【００１１】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、室温で簡便な操作で、析出酸素に妨
害されずに格子間酸素濃度を正確に測定することができ
る酸素析出したシリコン単結晶中の格子間酸素濃度測定
方法を提供することにある。An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a simple operation at room temperature and an oxygen precipitation method capable of accurately measuring an interstitial oxygen concentration without being hindered by precipitated oxygen. It is an object of the present invention to provide a method for measuring the interstitial oxygen concentration in a silicon single crystal.
【００１２】[0012]
【課題を解決するための手段】本発明は、酸素析出した
シリコン単結晶中の格子間酸素濃度を赤外吸収法により
測定するにあたり、室温で１７２０ｃｍ-1に現れるシリ
コン格子のフォノン結合 ＴＡ＋ＴＯとＳｉ2 Ｏの逆対
称伸縮振動モードとの結合に基づく吸収ピーク[B. Pajo
t et al., J. Electrochem. Soc., 132, 3034 (1985)]
のピーク高さ、面積、あるいは（半値幅）×（ピーク高
さ）の値によりシリコン単結晶中の格子間酸素濃度を測
定することを特徴とする。According to the present invention, when measuring the interstitial oxygen concentration in an oxygen-precipitated silicon single crystal by an infrared absorption method, a phonon bond of a silicon lattice appearing at 1720 cm -1 at room temperature, TA + TO and Si Absorption peak based on coupling of 2 O with antisymmetric stretching vibration mode [B. Pajo
t et al., J. Electrochem. Soc., 132, 3034 (1985)]
The interstitial oxygen concentration in the silicon single crystal is measured by the peak height, the area, or the value of (half width) × (peak height).
【００１３】更に空気中の水蒸気による赤外吸収は１７
２０ｃｍ-1のＯｉ吸収ピークと重なるため、本ピークを
利用してシリコン単結晶中の格子間酸素濃度を測定する
ためには水蒸気の吸収が現れないように、分光光度計の
装置内や試料室内を１７２０ｃｍ-1近傍に吸収を示さな
い雰囲気ガスによってパージすることを特徴とする。Further, infrared absorption by water vapor in the air is 17
Since this peak overlaps with the Oi absorption peak at 20 cm -1, the peak is used to measure the interstitial oxygen concentration in the silicon single crystal so that the absorption of water vapor does not appear. Is purged with an atmosphere gas exhibiting no absorption at around 1720 cm -1 .
【００１４】図２に示されるように、室温における１７
２０ｃｍ-1のＯｉピークの高さは１１０６ｃｍ-1のピー
ク高さと比べて１／５９と小さいが、高感度なフーリエ
変換型赤外分光分析装置（ＦＴ−ＩＲ）を用いれば、こ
の吸収ピークのピーク高さ、面積、あるいは（半値幅）
×（ピーク高さ）の値を充分に正確に測定できることが
判明し、本発明はこの事実に基づきなされたものであ
る。なお、本発明の方法は、アンチモンを高濃度に添加
したシリコン単結晶の格子間酸素濃度の測定にも可能で
ある。As shown in FIG.
The height of the Oi peak of 20 cm -1 is as small as 1/59 compared to the peak height of 1106cm -1, the use highly sensitive Fourier transform infrared spectroscopic analyzer (FT-IR), the absorption peak Peak height, area, or (half width)
It has been found that the value of x (peak height) can be measured sufficiently accurately, and the present invention has been made based on this fact. The method of the present invention can be used for measuring the interstitial oxygen concentration of a silicon single crystal to which antimony is added at a high concentration.
【００１５】[0015]
【作用】１７２０ｃｍ-1に現れるＯｉピークは、上記の
B. Pajot et al. の論文によれば、シリコン格子のフ
ォノン結合ＴＡ＋ＴＯとＳｉ2 Ｏの逆対称伸縮振動モー
ドとの結合に基づくものであるとされており、このピー
クは、図２にみられる１３００〜１０００ｃｍ-1の析出
酸素の吸収バンドと重なることがなく、従って格子間酸
素の吸収のみが関与している。よって、このピークのピ
ーク高さ、面積、あるいは（半値幅）×（ピーク高さ）
の値を用いることにより、析出酸素の存在するシリコン
単結晶中の格子間酸素濃度を正確に測定することができ
る。The Oi peak appearing at 1720 cm -1 is
According to a paper by B. Pajot et al., It is based on the coupling between the phonon coupling TA + TO of the silicon lattice and the antisymmetric stretching vibration mode of Si 2 O, and this peak is seen in FIG. It does not overlap with the absorption band of 1300-1000 cm -1 for the precipitated oxygen, and thus only absorption of interstitial oxygen is involved. Therefore, the peak height, area, or (half width) × (peak height) of this peak
By using the value of, the interstitial oxygen concentration in the silicon single crystal where the precipitated oxygen exists can be accurately measured.
【００１６】[0016]
【実施例】次に、実施例を挙げて本発明をさらに詳細に
説明する。 実施例１ チョクラルスキー法によりシリコン単結晶棒を引き上
げ、得られた単結晶棒をダイヤモンドソーにより切り出
し、ラッピング、ケミカルエッチング、洗浄、鏡面研磨
等を行い、２ｍｍ厚さの両面鏡面研磨シリコンスラブを
得た。この両面研磨シリコンスラブをＦＴ−ＩＲ測定装
置の試料室内に設置し、装置内及び試料室内を、水蒸気
の加圧露点が−７３℃以下の窒素ガスでフローさせ、窒
素ガスパージ状態にした。ＦＴ−ＩＲ測定は、１７２０
ｃｍ-1付近の水蒸気起因の吸収ピークが検出下限以下と
なったことを確認した後に開始した。Ｏｉ吸収の差スペ
クトルを求めるための参照結晶としては、Ｏｉ濃度が検
出下限以下、抵抗率１００Ωｃｍ、厚さ２ｍｍの両面鏡
面研磨の浮遊帯法（ＦＺ法）Ｓｉ単結晶を用い、得られ
た差スペクトルにおける１７２０ｃｍ-1吸収ピークのピ
ーク高さの値によりシリコン単結晶中の格子間酸素濃度
を求めた。濃度換算は、別に用意した酸素濃度標準Ｓｉ
単結晶試料に関する１７２０ｃｍ-1ピークの濃度検量線
により行われた。一方、３．８Ｋの低温でＦＴ−ＩＲ分
光光度計により酸素析出吸収バンドと格子間酸素吸収ピ
ークを分離する方法により〔Ｏｉ〕信頼値を求めた。な
お、この方法で得られた赤外吸収スペクトルを図４に示
す。次に、上記の室温での１７２０ｃｍ-1に表われる吸
収ピークのピーク高さより求めた〔Ｏｉ〕評価値を、
３．８ＫでのＯｉピーク分離により得られた〔Ｏｉ〕信
頼値と対応させた結果が図１である。本図から明らかな
ように、１７２０ｃｍ-1に表われる室温の吸収ピークの
ピーク高さによりシリコン単結晶中の格子間酸素濃度を
求める本方法を用いれば、酸素析出結晶においてもより
正確な〔Ｏｉ〕測定値を簡便に得ることができる。この
他、１７２０ｃｍ-1ピークの面積あるいは（半値幅）×
（ピーク高さ）による測定についても検討したが、ピー
ク高さによる測定と同様の結果が得られた。Next, the present invention will be described in more detail with reference to examples. Example 1 A silicon single crystal rod was pulled up by the Czochralski method, the obtained single crystal rod was cut out with a diamond saw, and lapping, chemical etching, washing, mirror polishing and the like were performed to obtain a double-sided mirror-polished silicon slab having a thickness of 2 mm. Obtained. This double-side polished silicon slab was placed in a sample chamber of an FT-IR measuring apparatus, and the inside of the apparatus and the sample chamber was flowed with a nitrogen gas having a dew point of pressurized water vapor of −73 ° C. or less, to be in a nitrogen gas purge state. FT-IR measurement is 1720
The process was started after confirming that the absorption peak caused by water vapor near cm -1 was lower than the lower detection limit. As a reference crystal for obtaining a difference spectrum of the Oi absorption, a floating zone method (FZ method) Si single crystal of double-sided mirror polishing having an Oi concentration of not more than the lower detection limit, a resistivity of 100 Ωcm, and a thickness of 2 mm was used. The interstitial oxygen concentration in the silicon single crystal was determined from the peak height of the 1720 cm -1 absorption peak in the spectrum. Concentration conversion is based on the oxygen concentration standard Si prepared separately.
The measurement was performed based on a concentration calibration curve of a 1720 cm -1 peak for a single crystal sample. On the other hand, at a low temperature of 3.8 K, the [Oi] reliability value was determined by a method of separating an oxygen precipitation absorption band and an interstitial oxygen absorption peak by an FT-IR spectrophotometer. FIG. 4 shows the infrared absorption spectrum obtained by this method. Next, the [Oi] evaluation value obtained from the peak height of the absorption peak appearing at 1720 cm −1 at room temperature was calculated as follows:
FIG. 1 shows the result corresponding to the [Oi] confidence value obtained by the Oi peak separation at 3.8K. As is clear from this figure, the use of this method for determining the interstitial oxygen concentration in a silicon single crystal from the peak height of the absorption peak at room temperature appearing at 1720 cm −1 enables more accurate [Oi ] A measured value can be easily obtained. In addition, the area of 1720 cm -1 peak or (half width) ×
Although the measurement by (peak height) was also examined, the same result as the measurement by peak height was obtained.
【００１７】比較例１，２ 実施例１と同じ両面鏡面研磨シリコンスラブにつき、Ｆ
Ｔ−ＩＲ分光光度計により赤外吸収スペクトルを得た。
結果を図２に示す。この赤外吸収スペクトルにつき１３
００ｃｍ-1〜９００ｃｍ-1間にベースラインを引き、こ
のベースラインからのピーク高さから（社）日本電子工
業振興協会(JEIDA) によって標準化された濃度換算法
[T. Iizuka et. al., J. Electrochem. Soc., 132, 170
7 (1985)] に従って格子間酸素濃度〔Ｏｉ〕の評価値を
得た（Ａ法：比較例１）。この〔Ｏｉ〕評価値を３．８
ＫでのＯｉピークの分離により得られた〔Ｏｉ〕信頼値
と対応させてプロットした。結果を図３に○印で示す。
また、上記赤外吸収スペクトルにつき、１１５０ｃｍ-1
〜１０５０ｃｍ-1間にベースラインを引き、このベース
ラインからのピーク高さから同様に格子間酸素濃度〔Ｏ
ｉ〕の評価値を得た（Ｂ法：比較例２）。この〔Ｏｉ〕
評価値を３．８ＫでのＯｉピークの分離により得られた
〔Ｏｉ〕信頼値と対応させてプロットした。結果を図３
に△印で示す。図３から明らかなように、比較例１（Ａ
法）及び比較例２（Ｂ法）では〔Ｏｉ〕信頼値からの偏
寄が大きい。これは、１１０６ｃｍ-1の格子間酸素に基
づく吸収ピークが酸素析出に基づく吸収ピークと重な
り、上記両法ではこの重なりを分離せずに〔Ｏｉ〕評価
値を求めていることに起因するものである。Comparative Examples 1 and 2 For the same double-sided mirror-polished silicon slab as in Example 1,
An infrared absorption spectrum was obtained with a T-IR spectrophotometer.
The results are shown in FIG. 13 for this infrared absorption spectrum
A baseline is drawn between 00 cm -1 and 900 cm -1, and a concentration conversion method standardized by the Japan Electronic Industry Development Association (JEIDA) from the peak height from this baseline
[T. Iizuka et. Al., J. Electrochem. Soc., 132, 170
7 (1985)], the evaluation value of the interstitial oxygen concentration [Oi] was obtained (Method A: Comparative Example 1). This [Oi] evaluation value is 3.8
Plots were made in correspondence with the [Oi] confidence values obtained by separation of the Oi peak at K. The results are shown by a circle in FIG.
Further, regarding the infrared absorption spectrum, 1150 cm −1
A base line is drawn between ５０1050 cm −1, and the interstitial oxygen concentration [O
i) was obtained (Method B: Comparative Example 2). This [Oi]
The evaluation value was plotted in correspondence with the [Oi] confidence value obtained by separating the Oi peak at 3.8K. Fig. 3 shows the results.
Is indicated by a triangle. As is clear from FIG. 3, Comparative Example 1 (A
Method) and Comparative Example 2 (method B), the deviation from the [Oi] reliability value is large. This is due to the fact that the absorption peak based on interstitial oxygen at 1106 cm -1 overlaps with the absorption peak based on oxygen precipitation, and in both methods the [Oi] evaluation value is obtained without separating this overlap. is there.
【００１８】[0018]
【発明の効果】以上の説明から明らかなように、本発明
によれば、酸素析出したシリコン単結晶中の格子間酸素
濃度を、室温において簡易な操作で、析出酸素による妨
害を受けることなく、正確に測定することができる。As is apparent from the above description, according to the present invention, the interstitial oxygen concentration in the oxygen-precipitated silicon single crystal can be easily controlled at room temperature without being hindered by the precipitated oxygen. It can be measured accurately.
【図１】本発明の方法で得られた格子間酸素濃度〔Ｏ
ｉ〕の評価値と３．８Ｋでの低温測定法による〔Ｏｉ〕
信頼値との対応関係を示すグラフである。FIG. 1 shows the interstitial oxygen concentration [O
i] and the low-temperature measurement method at 3.8K [Oi]
It is a graph which shows the correspondence with a reliability value.
【図２】室温における酸素析出したシリコン単結晶のＦ
Ｔ−ＩＲによる赤外吸収スペクトルとＡ法及びＢ法のベ
ースラインを示すグラフである。FIG. 2 shows F of oxygen-precipitated silicon single crystal at room temperature.
It is a graph which shows the infrared absorption spectrum by T-IR, and the baseline of method A and method B.
【図３】Ａ法及びＢ法による格子間酸素濃度〔Ｏｉ〕の
評価値と３．８Ｋでの低温測定法による〔Ｏｉ〕信頼値
との対応関係を示すグラフである。FIG. 3 is a graph showing a correspondence relationship between an evaluation value of an interstitial oxygen concentration [Oi] by a method A and a method B and a [Oi] reliability value by a low-temperature measurement method at 3.8K.
【図４】酸素析出したシリコン単結晶について、３．８
Ｋの低温で得られた赤外吸収スペクトル及びＯｉ吸収ピ
ークと酸素析出吸収バンドとの分離を示すグラフであ
る。FIG. 4 shows a graph of 3.8 oxygen-precipitated silicon single crystal.
5 is a graph showing an infrared absorption spectrum obtained at a low temperature of K and a separation between an Oi absorption peak and an oxygen precipitation absorption band.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−106947（ＪＰ，Ａ) 特開 平４−105046（ＪＰ，Ａ) 特開 昭56−94243（ＪＰ，Ａ) 特開 平１−195345（ＪＰ，Ａ) 特開 平３−82938（ＪＰ，Ａ) 特開 平２−196945（ＪＰ，Ａ) 特公 平４−12415（ＪＰ，Ｂ２) 特公 昭60−42905（ＪＰ，Ｂ２) ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-106947 (JP, A) JP-A-4-105046 (JP, A) JP-A-56-9243 (JP, A) JP-A-1- 195345 (JP, A) JP-A-3-82938 (JP, A) JP-A-2-196945 (JP, A) JP-B 4-12415 (JP, B2) JP-B 60-42905 (JP, B2)
Claims (2)
酸素濃度を赤外吸収法により測定するにあたり、１７２
０ｃｍ-1に現れる吸収ピークのピーク高さ、面積、ある
いは（半値幅）×（ピーク高さ）の値によりシリコン単
結晶中の格子間酸素濃度を測定することを特徴とする酸
素析出したシリコン単結晶中の格子間酸素濃度測定方
法。1. A method for measuring an interstitial oxygen concentration in an oxygen-precipitated silicon single crystal by an infrared absorption method.
Measuring the interstitial oxygen concentration in the silicon single crystal based on the peak height and area of the absorption peak appearing at 0 cm -1 or the value of (half width) × (peak height). A method for measuring the interstitial oxygen concentration in a crystal.
ージガス雰囲気下で測定を行う請求項１記載の酸素析出
したシリコン単結晶中の格子間酸素濃度測定方法。2. The method for measuring the interstitial oxygen concentration in an oxygen-precipitated silicon single crystal according to claim 1, wherein the measurement is performed in a purge gas atmosphere having no infrared absorption near 1720 cm −1 .
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14487992A JP2696290B2 (en) | 1992-05-11 | 1992-05-11 | Method for measuring interstitial oxygen concentration in oxygen-precipitated silicon single crystal |
| US08/038,694 US5386118A (en) | 1992-05-11 | 1993-03-29 | Method and apparatus for determination of interstitial oxygen concentration in silicon single crystal |
| EP97110093A EP0803725A1 (en) | 1992-05-11 | 1993-03-30 | Method and apparatus for determination of interstitial oxygen concentration in silicon single crystal |
| DE69316434T DE69316434T2 (en) | 1992-05-11 | 1993-03-30 | Method and device for determining the interstitial oxygen concentration in monocrystalline silicon |
| EP93302449A EP0570100B1 (en) | 1992-05-11 | 1993-03-30 | Method and apparatus for determination of interstitial oxygen concentration in silicon single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14487992A JP2696290B2 (en) | 1992-05-11 | 1992-05-11 | Method for measuring interstitial oxygen concentration in oxygen-precipitated silicon single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05312721A JPH05312721A (en) | 1993-11-22 |
| JP2696290B2 true JP2696290B2 (en) | 1998-01-14 |
Family
ID=15372507
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14487992A Expired - Lifetime JP2696290B2 (en) | 1992-05-11 | 1992-05-11 | Method for measuring interstitial oxygen concentration in oxygen-precipitated silicon single crystal |
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| Country | Link |
|---|---|
| JP (1) | JP2696290B2 (en) |
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|---|---|---|---|---|
| JP3446572B2 (en) * | 1997-11-11 | 2003-09-16 | 信越半導体株式会社 | Method for determining oxygen precipitation behavior in silicon single crystal, method for determining silicon single crystal wafer manufacturing process, and recording medium storing program |
| JP2002174593A (en) * | 2000-12-06 | 2002-06-21 | Memc Japan Ltd | Method for evaluating single-crystal ingot, and method for cutting single crystal ingot using the same |
| JP6979007B2 (en) * | 2018-12-17 | 2021-12-08 | グローバルウェーハズ・ジャパン株式会社 | Ultra-low oxygen concentration measurement method for silicon wafers |
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|---|---|---|---|---|
| JPH01195345A (en) * | 1988-01-29 | 1989-08-07 | Fujitsu Ltd | Method for evaluating silicon crystal |
| JP2960474B2 (en) * | 1990-04-05 | 1999-10-06 | 日本たばこ産業株式会社 | Nicotine sensor |
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