JP6973361B2 - Oxygen concentration measurement method - Google Patents

Description

The present invention relates to a method for measuring an oxygen concentration in a silicon single crystal.

There is a low temperature photoluminescence (PL) method as a method for measuring the impurity concentration in a silicon single crystal with high sensitivity.
In the method for quantifying oxygen concentration by the low temperature PL method, Patent Document 1 irradiates a sample with an electron beam and carbon ion or oxygen ion (particle beam) to form a composite defect, and obtains the luminescence intensity caused by the composite defect. A method of measuring and quantifying the oxygen concentration from the intensity thereof is disclosed.

Further, in the carbon concentration quantification method by the low temperature PL method, for example, Non-Patent Document 1 and Patent Document 1 are irradiated with an ion beam of an electron beam, carbon ion or oxygen ion on a sample to form a composite defect, and the composite defect is formed. A method of measuring the resulting luminescence intensity and quantifying the carbon concentration from the intensity is disclosed.
Patent Document 2 describes a value obtained by standardizing a luminescence spectrum (W line) derived from interstitial silicon (I) introduced by irradiating a silicon single crystal with an electron beam and a light emitting line (TO line) derived from silicon. , A method of preparing a calibration curve between the carbon concentrations in a silicon single crystal and quantifying the carbon concentration from the W line / TO line obtained by the luminescence method is disclosed.
In Patent Document 3, ions other than carbon and oxygen are injected into a silicon single crystal, and the luminescence spectral intensity of interstitial carbon, G-ray (Ci-Cs), or C-line (Ci-Oi) formed by the injection. And, a method of creating a calibration curve between carbon concentrations and quantifying the carbon concentration from the spectral intensity of carbon-related composite defects is disclosed.

As a method for measuring the oxygen concentration in a silicon single crystal, an FT-IR method or a SIMS method is generally used. The lower limit of detection is 0.07 (ppma-JEITA) in the FT-IR method and 0.02 (ppma) in the SIMS method.

Japanese Unexamined Patent Publication No. 04-344443 JP-A-2015-1111615 JP-A-2015-156420 Japanese Unexamined Patent Publication No. 2015-101259

M. Nakamura et al. , J. Electochem. Soc. 141,3576 (1994)

There is a low temperature PL method as a method for measuring the impurity concentration with high sensitivity by measuring the strength of the composite defect formed in the silicon single crystal, but as described above, most of them are carbon concentration measuring methods. In this, a calibration curve is created between the intensity ratio of the generated G-ray and C-ray and the concentration ratio of the carbon concentration and the oxygen concentration in the silicon single crystal by irradiating the silicon single crystal with an electron beam. There is also a method of measuring the carbon concentration from the oxygen concentration in the silicon single crystal and the intensity ratio of G-ray and C-ray (Patent Document 4). After preparing multiple silicon single crystals with known carbon concentrations and different carbon concentrations, measuring the luminescence intensity of the composite defect, and creating a calibration curve with the carbon concentration, the composite of the measurement samples to be measured is finally used. This is a method of quantifying the carbon concentration in a silicon single crystal by measuring the luminescence intensity of a defect and applying it to the calibration curve.

Here, the present inventor has found that the above-mentioned method for measuring carbon concentration is also applied to the measurement of oxygen concentration. At this time, in particular, when measuring the oxygen concentration from the carbon concentration in the silicon single crystal and the intensity ratio (and proportionality constant) of G-ray and C-ray, the irradiation amount of the particle beam is adjusted as necessary to obtain the luminous spectrum. The peak intensity may be increased (Japanese Patent Application No. 2018-42902). However, even when the particle beam irradiation amount is changed in this way, a plurality of samples having known carbon concentration and oxygen concentration are prepared again, and under the changed particle beam irradiation amount, a new proportionality such as Japanese Patent Application No. 2018-42902 is obtained. There is a problem that the oxygen concentration can be obtained only after performing the complicated work of obtaining the constant.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a method for easily measuring the oxygen concentration in a silicon single crystal.

In order to achieve the above object, the present invention uses the G-ray intensity and C-ray intensity obtained by PL measurement or CL measurement of a silicon single crystal irradiated with a particle beam, and the separately determined carbon concentration. It is an oxygen concentration measuring method for measuring the oxygen concentration in a single crystal.
The oxygen concentration in the silicon single crystal is determined by the following formula: oxygen concentration = proportionality constant × carbon concentration × (C-line intensity / G-line intensity) ... (A)
When measuring with
The first proportionality constant α1, which is the proportionality constant of the formula (A), under the first particle beam irradiation condition is obtained in advance.
Next, prepare a sample of silicon single crystal and prepare it.
PL measurement or CL measurement was performed under the same first particle beam irradiation conditions as when the first proportionality constant α1 was obtained, and G-ray intensity G1 and C-line intensity C1 were obtained, and
PL measurement or CL measurement was performed under a second particle beam irradiation condition different from the first particle beam irradiation condition, and G-ray intensity G2 and C-ray intensity C2 were obtained.
Then, under the second particle beam irradiation condition, the second proportionality constant α2, which is the proportionality constant of the equation (A), is changed to the following equation: proportionality constant α2 = proportionality constant α1 × {(C line intensity C1 / G line). Strength G1) / (C line strength C2 / G line strength G2)} ... (B)
Determined from
An oxygen concentration measuring method characterized by measuring the oxygen concentration in the silicon single crystal under the second particle beam irradiation condition by using the formula (A) in which the determined proportionality constant α2 is substituted. offer.

With such an oxygen concentration measuring method, when determining the second proportionality constant α2, the oxygen concentration and carbon concentration of the sample to be used are obtained as in Japanese Patent Application No. 2018-42902, and G-rays are further measured by PL measurement or the like. The second proportionality constant α2 under the second particle beam irradiation condition can be easily and accurately obtained without performing complicated work such as obtaining the intensity and C-ray intensity.
Then, according to the formula (A) using the second proportionality constant α2, the oxygen concentration can be measured easily and with high accuracy under the second particle beam irradiation condition.

At this time, the second particle beam irradiation condition can be a condition in which only the particle beam irradiation amount is changed from the first particle beam irradiation condition.

By doing so, conditions other than the particle beam irradiation amount, for example, the particle beam and its acceleration voltage are not changed, so that the second proportionality constant α2 can be obtained with higher accuracy.

Further, as a sample of the silicon single crystal,
From one silicon single crystal wafer, two wafer pieces taken from the same distance from the center of the silicon single crystal wafer were prepared.
PL measurement or CL measurement under the first particle beam irradiation condition is performed on one of the two wafer pieces.
The PL measurement or CL measurement under the second particle beam irradiation condition can be performed on the other side.

By doing so, the carbon concentration and oxygen concentration of the above two wafer pieces can be regarded as the same. Therefore, when determining the second proportionality constant α2, the carbon concentration and oxygen concentration of the sample used should be obtained more reliably. Instead, the second proportionality constant α2 can be obtained by the equation (B).

Alternatively, as PL measurement or CL measurement under the second particle beam irradiation condition,
Difference between the particle beam irradiation amount under the first particle beam irradiation condition and the particle beam irradiation amount under the second particle beam irradiation condition on the silicon single crystal sample irradiated with the particle beam under the first particle beam irradiation condition. Can be performed by additional irradiation.

By doing so, since the sample to be irradiated with the particle beam under the first particle beam irradiation condition and the second particle beam irradiation condition is the same, when determining the second proportionality constant α2, more reliably. The second proportionality constant α2 can be obtained by the formula (B) without obtaining the carbon concentration and the oxygen concentration of the sample used. In particular, this method is effective when it is desired to increase the particle beam irradiation amount of the second particle beam irradiation condition more than the particle beam irradiation amount of the first particle beam irradiation condition.

At this time, the particle beam irradiation amount under the second particle beam irradiation condition shall be 2 to 10 times, or 0.1 to 0.5 times, the particle beam irradiation amount under the first particle beam irradiation condition. Can be done.

As described above, if the irradiation amount of the first particle beam irradiation condition is not optimal, it may be necessary to increase or decrease the irradiation amount. If the first particle beam irradiation condition is a condition that is normally used, it is already a condition that is appropriate to some extent in preliminary experiments, etc. Therefore, for example, when increasing the irradiation amount under the second particle beam irradiation condition, it is 2 to 10 times. Irradiation amount of is sufficient. On the contrary, when the irradiation amount is reduced, the irradiation amount of 0.1 to 0.5 times is sufficient.

Further, the oxygen concentration in the silicon single crystal to be measured can be set to ^{1 × 10 14} atoms / cm ^{3 or more.}

As described above, according to the measuring method of the present invention, even ^{a low oxygen concentration of 1 × 10 14} atoms / cm ³ can be easily and accurately obtained.

As described above, in the case of the oxygen concentration measuring method of the present invention, when determining the second proportionality constant, complicated work such as measuring the carbon concentration and the oxygen concentration of the sample to be used as in Japanese Patent Application No. 2018-42902 is complicated. The second proportionality constant α2 under the second particle beam irradiation condition can be easily and accurately obtained without performing the above. Then, by using the formula (A) using the second proportionality constant α2, the oxygen concentration can be measured easily and with high accuracy under the second particle beam irradiation condition.

It is a flow chart which shows an example of the process of the oxygen concentration measuring method of this invention. It is a graph which shows the relationship between (C line intensity C1 / G line intensity G1) and (C line intensity C2 / G line intensity G2) in Example 1. FIG. It is a graph which shows the relationship between the oxygen concentration obtained from the 1st particle beam irradiation condition and the oxygen concentration obtained from the 2nd particle beam irradiation condition in Example 1. FIG. It is a graph which shows the relationship between the proportionality constant β and the oxygen concentration obtained from each sample in the comparative example 1. FIG.

Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.
As mentioned above, the formula (A), that is,
Oxygen concentration = proportionality constant x carbon concentration x (C-line intensity / G-line intensity) ... (A)
When determining the oxygen concentration using, it is necessary to determine the proportionality constant in advance, determine the type of particle beam and its irradiation amount by considering various conditions, and the oxygen concentration and carbon concentration differ under the determined conditions. The sample was irradiated with a particle beam, and the proportionality constant of the formula (A) was determined from the obtained G-ray intensity, C-ray intensity, carbon concentration of each sample, and oxygen concentration.

In this way, while determining the oxygen concentration in the silicon single crystal using the formula (A), the peak of either one or both of the G line and the C line is weak, and the peak intensity is increased by increasing the irradiation amount. There may be a need to increase it. On the contrary, the determined irradiation amount may be too strong, and the structure of the silicon single crystal may be disturbed to weaken the peak. In this case, it may be necessary to reduce the irradiation amount to increase the peak intensity. ..

However, if the irradiation amount of the particle beam is changed, the proportionality constant used before the irradiation amount change cannot be used in the formula (A), and the proportionality before the irradiation amount change is determined in order to determine a new proportionality constant. It required the same complicated work as when determining the constant.

Therefore, the present inventor conducted diligent research and found that the proportionality constant before the change of the particle beam irradiation amount (the first proportionality constant α1 under the first particle beam irradiation condition) and the proportionality constant after the change of the irradiation amount (the second). By using the relational expression with the second proportionality constant α2) in the particle beam irradiation condition, the second particle beam irradiation condition with high accuracy can be performed without performing complicated work as in Japanese Patent Application No. 2018-42902. It was found that the proportionality constant α2 of 2 can be obtained. The relational expression derived by the present inventor is as follows.
Proportional constant α2 = Proportional constant α1 × {(C line strength C1 / G line strength G1) / (C line strength C2 / G line strength G2)} ... (B)
Further, they have found that the oxygen concentration under the second particle beam irradiation condition can be easily measured by the formula (A) using the second proportionality constant α2, and completed the present invention.

FIG. 1 shows an example of the process of the oxygen concentration measuring method of the present invention.
(Step 1: Determination of the first proportionality constant α1)
First, the G-ray intensity [a. u. ], C-line intensity [a. u. ], And using the separately determined carbon concentration [atoms / cm ³ ] and oxygen concentration [ppma-JEITA],
Oxygen concentration = proportionality constant x carbon concentration x (C-line intensity / G-line intensity) ... (A)
The proportionality constant that becomes is obtained in advance.
Although the PL method is used to explain the process of the oxygen concentration measuring method of the present invention, the CL (cathodoluminescence) method can also be used instead.

Specifically, 15 levels of silicon single crystal substrates (samples for determining the proportionality constant) having different carbon concentrations and oxygen concentrations are prepared. At this time, in order to improve the accuracy of the derived proportionality constant, it is preferable to prepare 5 levels or more.
Then, the carbon concentration and the oxygen concentration of these samples are measured by the SIMS method (or FT-IR method or the like). Then, each silicon single crystal substrate is irradiated with an electron beam ^{of 1.0 × 10 15} ejectrons / cm ² at an acceleration voltage of 2 MV by an electron beam irradiator. These conditions are defined as the first particle beam irradiation conditions. In this way, G-rays and C-lines are formed on the silicon single crystal substrate, and their peak intensities are measured by the PL method. The sample temperature at this time is the liquid helium temperature.

In these silicon single crystal substrates, the obtained carbon concentration, oxygen concentration, G-ray intensity, and C-ray intensity are substituted into the above equation (A), and the average value of the obtained proportionality constants is the first proportionality constant α1. And. In this way, 2.25 × 10 ^-15 ppma / (atoms / cm ³ ) was obtained as the first proportionality constant α1.
The above-mentioned first particle beam irradiation condition and the first proportionality constant α1 are examples, and are not limited to these conditions and numerical values, and can be appropriately determined.

(Step 2: Determination of the second proportionality constant α2)
After determining the first proportionality constant α1 under the first particle beam irradiation condition as described above, usually, the particle beam is normally applied to the silicon single crystal to be measured for the actual oxygen concentration under the first particle beam irradiation condition. The oxygen concentration can be obtained by substituting the G-ray intensity, the C-ray intensity, the separately obtained carbon concentration, and the first proportionality constant α1 obtained by irradiation with the equation (A).

However, as described above, it may be necessary to adjust the irradiation amount of the particle beam in the intensity measurement of the C ray or the like under the first particle beam irradiation condition. By increasing or decreasing the irradiation amount of the particle beam, it may be possible to quantify the oxygen concentration at a lower concentration. In this case, if a sample for determining the proportionality constant in which the irradiation amount of the particle beam is changed is prepared as in Japanese Patent Application No. 2018-42902 and the same complicated method as described above is performed, the proportionality corresponding to the condition after changing the irradiation amount is performed. It is possible to obtain a constant, but it is necessary to obtain the carbon concentration and oxygen concentration of the sample.

However, when the carbon concentration and oxygen concentration of the sample for determining the proportionality constant are equal to the first particle beam irradiation condition and the second particle beam irradiation condition, the following is clarified as a result of examining the formula (A) in more detail. It became.
Let G1 and C1 be the G-ray intensity and C-ray intensity under the first particle beam irradiation condition, and G2 and C2 be the G-ray intensity and C-line intensity under the second particle beam irradiation condition.
Oxygen concentration = proportionality constant α1 x carbon concentration x (C-line intensity C1 / G-line intensity G1)
= Proportional constant α2 × carbon concentration × (C line intensity C2 / G line intensity G2)
Therefore, when the proportionality constant α2 is solved, the following equation (B) is obtained.
Proportional constant α2 = Proportional constant α1 × {(C line strength C1 / G line strength G1) / (C line strength C2 / G line strength G2) ... (B)
That is, since the formula (B) does not include the carbon concentration and the oxygen concentration, if the proportionality constant α1 is known, a sample for determining the proportionality constant is prepared as in Japanese Patent Application No. 2018-42902. The proportionality constant α2 can be obtained without having to bother to measure the carbon concentration and the oxygen concentration of the sample for determining the proportionality constant. When obtaining a new second proportionality constant α2 under a new second particle beam irradiation condition, it is possible to easily and highly accurately obtain the proportionality constant α2 without the complicated work as in the past.

Hereinafter, the specific procedure for determining the second proportionality constant α2 will be described in more detail.
A sample of a silicon single crystal is prepared, and PL measurement or CL measurement is performed under the same first particle beam irradiation conditions as when the first proportionality constant α1 is obtained, and G-ray intensity G1 and C-line intensity C1 are obtained. Further, PL measurement or CL measurement is performed under a second particle beam irradiation condition different from the first particle beam irradiation condition, and G-ray intensity G2 and C-ray intensity C2 are obtained.

The first particle beam irradiation condition and the second particle beam irradiation condition itself are not particularly limited and can be appropriately determined. At this time, the second particle beam irradiation condition may be different from the first particle beam irradiation condition, for example, the type of particle beam, the acceleration voltage, the irradiation amount, and the incident angle.
Further, the first particle beam irradiation condition can be the same as that at the time of normal oxygen concentration measurement, in addition to the above-mentioned example.
Further, it is more preferable that the second particle beam irradiation condition differs from the first particle beam irradiation condition only in the particle beam irradiation amount. Here, since the first particle beam irradiation condition is usually already suitable to some extent in a preliminary experiment or the like, especially when only the first particle beam irradiation amount is changed as the second particle beam irradiation condition. This is a fine adjustment from the first particle beam irradiation condition, and when increasing the irradiation amount, it is sufficient to select from 2 to 10 times the irradiation amount. The same applies when reducing the irradiation amount, and it is sufficient to select from 0.1 to 0.5 times the irradiation amount.
For example, if the peak of the C-ray intensity is weak when an electron beam ^{of 1 × 10 15} ejectrons / cm ² is irradiated as the first particle beam irradiation condition as in the above-mentioned example, the second particle beam is used. As the irradiation condition, the electron beam irradiation amount can be 5 × 10 ¹⁵ ejectrons / cm ² .

As described above, if the second particle beam irradiation condition is a condition in which only the particle beam irradiation amount is changed from the first particle beam irradiation condition, conditions other than the particle beam irradiation amount, for example, the particle beam and its acceleration voltage, etc. Since does not change, the second proportionality constant α2 can be obtained with higher accuracy.

Here, an example of how to prepare a sample for determining the proportionality constant of a silicon single crystal and how to measure PL under the first particle beam irradiation condition and the second particle beam irradiation condition will be given.
First, as a sample for determining the proportionality constant of a silicon single crystal, two wafer pieces taken from one silicon single crystal wafer at the same distance from the center of the silicon single crystal wafer are prepared. Then, the PL measurement under the first particle beam irradiation condition is performed on one of the two wafer pieces to obtain the G-ray intensity G1 and the C-line intensity C1. Then, the PL measurement under the second particle beam irradiation condition is performed on the other side, and the G-ray intensity G2 and the C-line intensity C2 are obtained.
With this method, the carbon concentration and oxygen concentration of the two prepared wafer pieces can be regarded as the same, and the second proportionality constant α2 can be easily obtained by the equation (B) more reliably. When obtaining the second proportionality constant α2, it is not necessary to separately measure the carbon concentration and the oxygen concentration of the sample as in Japanese Patent Application No. 2018-42902, which is convenient.

As another example, one sample of a silicon single crystal is prepared, and the particle beam is irradiated to the sample under the first particle beam irradiation condition to perform PL measurement, and the G line intensity G1 and the C line intensity C1 are obtained. Next, the sample of the silicon single crystal irradiated with the particle beam under the first particle beam irradiation condition was subjected to the particle beam irradiation amount under the first particle beam irradiation condition and the particle beam irradiation amount under the second particle beam irradiation condition. PL measurement is performed by additionally irradiating the difference, and G-ray intensity G2 and C-line intensity C2 are obtained.
In such a method, since the same sample is used, the carbon concentration and the oxygen concentration are naturally the same, and the second proportionality constant α2 can be easily obtained by using the formula (B). In particular, it is an effective method when it is desired to increase the particle beam irradiation amount of the second particle beam irradiation condition more than the particle beam irradiation amount of the first particle beam irradiation condition.
On the contrary, if it is desired to reduce the particle beam irradiation amount of the second particle beam irradiation condition from the particle beam irradiation amount of the first particle beam irradiation condition, the PL measurement is first performed under the second particle beam irradiation condition. Next, the difference in the amount of particle beam irradiation between the first particle beam irradiation condition and the second particle beam irradiation condition may be additionally irradiated, and PL measurement may be performed under the first particle beam irradiation condition.

In addition to these, samples of silicon single crystals, which are known to have the same carbon concentration and oxygen concentration from past data, are used for the first particle beam irradiation condition and for the second particle beam irradiation condition, respectively. You can also prepare it.
Alternatively, two samples taken from adjacent locations in one silicon single crystal wafer can be used.
In either method, the carbon concentration and the oxygen concentration of the sample under the first particle beam irradiation condition and the second particle beam irradiation condition are the same or can be regarded as the same. Therefore, the equation (B) can be used.
Then, by substituting the first proportionality constant α1, G-line intensity G1, C-line intensity C1, G-line intensity G2, and C-line intensity C2 into the equation (B), the second proportionality constant α2 can be easily obtained. ..

(Step 3: Oxygen concentration measurement under the second particle beam irradiation condition)
Using the formula (A) in which the second proportionality constant α2 is substituted, the oxygen concentration in the silicon single crystal is measured under the second particle beam irradiation condition. That is, by further substituting the separately obtained carbon concentration of the silicon single crystal to be measured and the G-ray intensity G2 and C-ray intensity C2 under the second particle beam irradiation condition into the formula (A), the silicon single crystal can be used. The oxygen concentration can be obtained.

With such a measurement method of the present invention, by optimizing from the first particle beam irradiation condition to the second particle beam irradiation condition, which is a more appropriate measurement condition, 1 × 10 ¹⁴ atoms / cm. It is possible to easily and accurately obtain a low oxygen concentration of ^{3 or more.}

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited thereto.
(Example 1)
As described above, the particle beam irradiation condition is an acceleration voltage of 2 MV, the electron beam (EB) irradiation amount is 1 × 10 ¹⁵ ejectrons / cm ² (first particle beam irradiation condition), and the sample temperature at the time of PL measurement is In the case of liquid helium temperature, the first proportionality constant α1 of the formula (A) is determined to be ^{2.25 × 10 -15} ppma / (atoms / cm ^3).

Next, in order to obtain the second proportionality constant α2 when the EB irradiation amount is 5 × 10 ¹⁵ electrons / cm ² (second particle beam irradiation condition), from one silicon wafer from the center thereof. Three samples were cut out from the same distance position. These three samples can be regarded as having the same carbon concentration and oxygen concentration with each other.
The first of these was irradiation with an electron beam at an irradiation amount of ^{1 × 10 15} ejectrons / cm ² , which is the first particle beam irradiation condition. Secondly, the electron beam was irradiated with an irradiation amount of ^{5 × 10 15} ejectrons / cm ² , which is the second irradiation condition. In each case, the acceleration voltage of the electron beam was set to 2 MV. Next, PL measurement of each sample was performed at the liquid helium temperature, and the G-ray intensity G1 and C-ray intensity C1 under the first particle beam irradiation condition and the G-ray intensity G2 and C-ray under the second particle beam irradiation condition were performed. Strength C2 was obtained.
The third item was not used in Example 1 but was used in Comparative Example 1 described later.

PL measurements for the above two samples were performed on 19-level samples that are expected to have different carbon and oxygen concentrations, and {(C-line intensity C1 / G-line intensity G1) / (C-line intensity C2 / G). When the average value of the line strength G2)} was calculated, it was 0.779.
FIG. 2 plots the relationship between (C-line intensity C1 / G-line intensity G1) and (C-line intensity C2 / G-line intensity G2). As a reference, a graph with an inclination of 1 ((C line intensity C1 / G line intensity G1) = (C line intensity C2 / G line intensity G2)) is drawn with a solid line in FIG.
Therefore, for the second proportionality constant α2, the first proportionality constant α1 and the above average value are substituted into the equation (B), that is, 1.75 × 10 ^{− by 2.25 × 10 -15 × 0.779. It was determined to be 15} ppma / (atoms / cm ³ ).

Next, for the 19-level sample, the separately obtained carbon concentration, G-ray intensity G2, and C-line intensity C2 were substituted into the equation (A) into which the second proportionality constant α2 was substituted. As a result, the oxygen concentration under the second particle beam irradiation condition could be obtained.
Here, in the same manner, the oxygen concentration under the first particle beam irradiation condition (first proportional constant α1) is also obtained, and the oxygen concentration obtained from the first particle beam irradiation condition and the second particle beam irradiation condition are used. The obtained oxygen concentration is shown in a plot in FIG. 3 and compared. As a reference, a graph with a slope of 1 (oxygen concentration obtained from the first particle beam irradiation condition = oxygen concentration obtained from the second particle beam irradiation condition) is drawn with a solid line. As shown in FIG. 3, the two matched very well. That is, it can be seen that the second proportionality constant α2 is as accurate as the first proportionality constant α1 obtained by performing complicated work in the same manner as in Japanese Patent Application No. 2018-42902. Moreover, in obtaining the second proportionality constant α2, complicated work as in Japanese Patent Application No. 2018-42902 is not required, which is simple.

(Example 2)
In Example 1, an electron beam is irradiated under the first particle beam irradiation condition (acceleration voltage 2 MV, irradiation amount 1 × 10 ¹⁵ ejectrons / cm ² ), and PL measurement is performed at the liquid helium temperature (G-ray intensity G1, C-ray). To the sample subjected to the intensity C1), ^{electron beam irradiation of 4 × 10 15} ejectrons / cm ² was additionally performed at an acceleration voltage of 2 MV, and electron beam irradiation of 5 × 10 ¹⁵ ejectrons / cm ^{2 was performed in total.} I prepared a sample. The G-ray intensity G2 and the C-line intensity C2 at the liquid helium temperature of this were determined.

The average value of (C-line intensity C1 / G-line intensity G1) / (C-line intensity C2 / G-line intensity G2) of the 19-level sample was found to be 0.779.
Therefore, for the second proportionality constant α2, the first proportionality constant α1 and the above average value are substituted into the equation (B), that is, 1.75 × 10 ^{− by 2.25 × 10 -15 × 0.779. It was determined to be 15} ppma / (atoms / cm ³ ). In this way, the numerical values were the same as those in Example 1.

Next, the 19-level sample was obtained from the oxygen concentration obtained from the first particle beam irradiation condition (using the formula (A) in which the first proportionality constant α1 was substituted) and the second particle beam irradiation condition. When the oxygen concentrations (using the formula (A) in which the second proportionality constant α2 obtained as described above was substituted) were compared, the results shown in FIG. 3 were obtained as in Example 1, and the two were very well matched. bottom.

(Comparative Example 1)
Of the samples cut out in Example 1, the remaining one sample (that is, one x 19 levels) that had not been treated was used, and this was further divided into three to determine the carbon concentration of each sample. By the method, the oxygen concentration was determined by the FT-IR method. Then, electron beam irradiation of ^{5 × 10 15} ejectrons / cm ² was performed at an acceleration voltage of 2 MV. Next, PL measurement was performed at the liquid helium temperature to obtain G-line intensity and C-line intensity.

In each sample, the carbon concentration, oxygen concentration, G-ray intensity, and C-ray intensity are determined by the formula (A).
The proportionality constant was obtained by substituting into. The average value of this 19-level sample was 1.75 × 10 ^-15 ppma / (atoms / cm ³ ) (referred to as the proportionality constant β). FIG. 4 shows the relationship between the proportionality constant β obtained from each sample and the oxygen concentration. Although this value is the same as the second proportionality constant α2 of Example 1 and Example 2, it took a lot of time to obtain the carbon concentration and oxygen concentration of each sample. ..

Then, for the 19-level sample, the oxygen concentration obtained from the first particle beam irradiation condition (using the formula (A) in which the first proportionality constant α1 is substituted) and the oxygen obtained from the second particle beam irradiation condition. When the concentrations (using the formula (A) in which the proportionality constant β was substituted under the second particle beam irradiation condition obtained as described above) were compared, the two were in very good agreement. However, as described above, it took a long time to obtain the proportionality constant β under the second particle beam irradiation condition, so that the measurement as a whole took a long time.

(Example 3)
Prepare a sample (diameter 200 mm, FZ crystal, solidification rate = 20% position) collected from a silicon single crystal, and perform PL measurement at the liquid helium temperature under the same first particle beam irradiation conditions as in Example 1. went. As a result, the G-ray had a sufficient peak intensity under the first particle beam irradiation condition, but the C-ray peak was weak and the oxygen concentration could not be quantified.
A sample adjacent to this sample was prepared, EB irradiation was performed on the sample under the same second particle beam irradiation conditions as in Example 1, and PL measurement was performed at the liquid helium temperature. As a result, sufficient peak intensities were obtained for both G-line and C-line.
Therefore, using the formula (A) in which the second proportionality constant α2 (1.75 × 10 ^-15 ) under the second particle beam irradiation condition obtained in Example 1 was substituted, the carbon concentration separately obtained was obtained first. The oxygen concentration under the second particle beam irradiation condition was obtained by substituting the G-ray intensity and C-ray intensity in the PL measurement under the obtained second particle beam irradiation condition. As a result, 1.0 × 10 ¹⁴ atoms / It could be determined as cm ³ (that is, 0.002 ppma (JEITA)).

(Example 4)
A sample collected from a silicon single crystal (diameter 200 mm, FZ crystal, solidification rate = 20% position) (sample similar to Example 3) was prepared, and under the same first particle beam irradiation conditions as in Example 1. , PL measurement was performed at the liquid helium temperature. As a result, the G-ray had a sufficient peak intensity under the first particle beam irradiation condition, but the C-ray peak was weak and the oxygen concentration could not be quantified.
For this sample, the sample itself that had been EB-irradiated under the first particle beam irradiation conditions was additionally ^{irradiated with an electron beam of 4 × 10 15} electrons / cm ² at an acceleration voltage of 2 MV, for a total of 5 × 10 ¹⁵ electrons. A sample subjected to electron beam irradiation at / cm ^{2 was prepared.} This was measured by PL at the liquid helium temperature. As a result, sufficient peak intensities were obtained for both G-line and C-line.
Therefore, using the formula (A) in which the second proportionality constant α2 (1.75 × 10 ^-15 ) under the second particle beam irradiation condition obtained in Example 2 is substituted, the separately obtained carbon concentration is obtained first. and G-line intensity of the PL measurement of the second particle beam irradiation conditions, by substituting the C-ray intensity where to determine the oxygen concentration in the second particle beam irradiation conditions, 1.0 × ¹⁰ 14 atoms / cm ³ (that is, 0.002 ppma (JEITA)) could be determined.

(Comparative Example 2)
A sample collected from a silicon single crystal (diameter 200 mm, FZ crystal, solidification rate = 20% position) (sample similar to Example 3) was prepared, and under the same first particle beam irradiation conditions as in Example 1. , PL measurement was performed at the liquid helium temperature. As a result, the G-ray had a sufficient peak intensity under the first particle beam irradiation condition, but the C-ray peak was weak and the oxygen concentration could not be quantified.
A sample adjacent to this sample was prepared, EB irradiation was performed on the sample under the same particle beam irradiation conditions as in Comparative Example 1, and PL measurement was performed at the liquid helium temperature. As a result, sufficient peak intensities were obtained for both G-line and C-line.
Therefore, using the formula (A) in which the proportionality constant β (1.75 × ^10-15 ) obtained in Comparative Example 1 was substituted, the carbon concentration separately obtained and the previously obtained Comparative Example 1 were used. By substituting the G-ray intensity and C-ray intensity in the PL measurement under the same particle beam irradiation conditions, the oxygen concentration under the same particle beam irradiation conditions as in Comparative Example 1 was obtained. As a result, 1.0 × 10 ¹⁴ atoms / It could be determined as cm ³ (that is, 0.002 ppma (JEITA)).

As described above, Examples 1 and 2 and Examples 3 and 4 according to the present invention measure the oxygen concentration with at least the same high accuracy as Comparative Example 1 and Comparative Example 2 according to the method of Japanese Patent Application No. 2018-42902, respectively. I was able to. Further, if the second particle beam irradiation condition is adjusted, a lower oxygen concentration can be measured. Moreover, in Example 1-4, the complicated work as in Comparative Example 1-2 was eliminated, and the measurement could be performed easily in less time than in the conventional method.

The present invention is not limited to the above embodiment. The above embodiment is an example, and any one having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. It is included in the technical scope of the invention.

Claims (6)

Oxygen concentration measurement to measure the oxygen concentration in the silicon single crystal using the G-ray intensity and C-ray intensity obtained by PL measurement or CL measurement of the silicon single crystal irradiated with particle beam and the carbon concentration obtained separately. It ’s a method,
The oxygen concentration in the silicon single crystal is determined by the following formula: oxygen concentration = proportionality constant × carbon concentration × (C-line intensity / G-line intensity) ... (A)
When measuring with
The first proportionality constant α1, which is the proportionality constant of the formula (A), under the first particle beam irradiation condition is obtained in advance.
Next, prepare a sample of silicon single crystal and prepare it.
PL measurement or CL measurement was performed under the same first particle beam irradiation conditions as when the first proportionality constant α1 was obtained, and G-ray intensity G1 and C-line intensity C1 were obtained, and
PL measurement or CL measurement was performed under a second particle beam irradiation condition different from the first particle beam irradiation condition, and G-ray intensity G2 and C-ray intensity C2 were obtained.
Then, under the second particle beam irradiation condition, the second proportionality constant α2, which is the proportionality constant of the equation (A), is changed to the following equation: proportionality constant α2 = proportionality constant α1 × {(C line intensity C1 / G line). Strength G1) / (C line strength C2 / G line strength G2)} ... (B)
Determined from
A method for measuring an oxygen concentration, which comprises measuring the oxygen concentration in a silicon single crystal under the second particle beam irradiation condition by using the formula (A) in which the determined proportionality constant α2 is substituted. The oxygen concentration measuring method according to claim 1, wherein the second particle beam irradiation condition is a condition in which only the particle beam irradiation amount is changed from the first particle beam irradiation condition. As a sample of the silicon single crystal
From one silicon single crystal wafer, two wafer pieces taken from the same distance from the center of the silicon single crystal wafer were prepared.
PL measurement or CL measurement under the first particle beam irradiation condition is performed on one of the two wafer pieces.
The oxygen concentration measuring method according to claim 1 or 2, wherein the PL measurement or the CL measurement under the second particle beam irradiation condition is performed on the other side. As PL measurement or CL measurement under the second particle beam irradiation condition,
Difference between the particle beam irradiation amount under the first particle beam irradiation condition and the particle beam irradiation amount under the second particle beam irradiation condition on the silicon single crystal sample irradiated with the particle beam under the first particle beam irradiation condition. The oxygen concentration measuring method according to claim 1 or 2, wherein the method is carried out by additional irradiation. The particle beam irradiation amount under the second particle beam irradiation condition is 2 to 10 times, or 0.1 to 0.5 times, the particle beam irradiation amount under the first particle beam irradiation condition. The oxygen concentration measuring method according to any one of claims 1 to 4. The oxygen concentration measuring method according to any one of claims 1 to 5, wherein the oxygen concentration in the silicon single crystal to be measured is 1 × 10 ¹⁴ atoms / cm ^{3 or more.}

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