Method for heat-treating silicon single crystal wafer

Abstract

A method for heat-treating a silicon single crystal wafer to control a BMD density thereof to achieve a predetermined BMD density by performing an RTA heat treatment on a silicon single crystal wafer composed of an Nv region in a nitriding atmosphere, and then performing a second heat treatment, the method including: formulating a relational equation for a relation between BMD density and RTA temperature in advance; and determining an RTA temperature for achieving the predetermined BMD density according to the relational equation. Consequently, a method for heat-treating a silicon single crystal wafer for manufacturing an annealed wafer or an epitaxial wafer each having defect-free surface and a predetermined BMD density in a bulk portion thereof.

Claims

1. A method for heat-treating a silicon single crystal wafer to control a BMD density thereof to achieve a predetermined BMD density by performing an RTA heat treatment on a silicon single crystal wafer composed of an Nv region in a nitriding atmosphere, and then performing a second heat treatment, the method comprising: formulating a relational equation for a relation between BMD density and RTA temperature in advance, the relational equation being determined under the same condition as the nitriding atmosphere; and determining an RTA temperature for achieving the predetermined BMD density according to the relational equation, wherein the second heat treatment is performed under conditions within ranges of 850 to 950° C. and 2 hours or more and less than 32 hours, the nitriding atmosphere is an atmosphere containing ammonia, and an RTA temperature at which a predetermined BMD density is achieved is determined by using BMD density (/cm.sup.3)=3×10.sup.40 exp (−8.86 eV/kT) as the relational equation, and setting a control range of the predetermined BMD density to 1×10.sup.9 to 1×10.sup.11 /cm.sup.3.

2. The method for heat-treating a silicon single crystal wafer according to claim 1, wherein the RTA heat treatment is performed for a heat-treatment time of 1 second or more and less than 10 seconds.

3. The method for heat-treating a silicon single crystal wafer according to claim 1, wherein the silicon single crystal wafer has an oxygen concentration of 13 ppma (JEIDA) or more and less than 17 ppma (JEIDA).

4. The method for heat-treating a silicon single crystal wafer according to claim 2, wherein the silicon single crystal wafer has an oxygen concentration of 13 ppma (JEIDA) or more and less than 17 ppma (JEIDA).

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a graph showing a relational equation of BMD density and RTA temperature determined in the present invention.

(2) FIG. 2 is a graph which shows that the relational equation of the present invention holds.

DESCRIPTION OF EMBODIMENTS

(3) As described above, it has been conventional to perform an RTA heat treatment on a wafer, and then further perform a heat treatment for growing precipitate nuclei as a second heat treatment so as to form a DZ layer in the surface of the wafer and provide a desired BMD distribution in a bulk portion of the wafer.

(4) The present inventors have earnestly studied the above problem, and found that a predetermined relational equation between BMD density and RTA temperature can be achieved when an RTA treatment is performed in a nitriding atmosphere to implant vacancies, and then oxide precipitate nuclei formed by reaction of the vacancies and oxygen in the silicon single crystal are grown and stable BMDs are formed by the subsequent heat treatment. Thus, the present inventors have found that using this relational equation, a BMD density can be predicted from the RTA temperature, or an RTA temperature for controlling the BMD density to a predetermined BMD density can be determined. These findings have led to the completion of the present invention.

(5) That is, the present invention is a method for heat-treating a silicon single crystal wafer to control a BMD density thereof to achieve a predetermined BMD density by performing an RTA heat treatment on a silicon single crystal wafer composed of an Nv region in a nitriding atmosphere, and then performing a second heat treatment, the method comprising:

(6) formulating a relational equation for a relation between BMD density and RTA temperature in advance; and

(7) determining an RTA temperature for achieving the predetermined BMD density according to the relational equation.

(8) Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

(9) Note that the “RTA heat treatment” in the present invention is a rapid thermal annealing heat treatment, can be performed in a commercially available RTA heat treatment furnace, and is a heat treatment for implanting vacancies in a wafer and forming oxide precipitate nuclei by reaction with oxygen in the silicon single crystal. On the other hand, the “second heat treatment” is a heat treatment that is performed after the RTA heat treatment for growing and stabilizing the formed oxide precipitate nuclei.

(10) In the present invention, firstly, a plurality of Nv-region silicon single crystal wafers (CW wafers: chemically etched wafers) are prepared, and after making the RTA temperature vary under a nitriding atmosphere, are processed into PW wafers (mirror-polished wafers). Then, the second heat treatment is performed for growing and stabilizing oxide precipitate nuclei, and the BMD density in the bulk of each silicon single crystal wafer is measured. Note that an Nv region is a neutral (N) region having no excess or deficiency of atoms where vacancies (vacancy) are dominant. Since vacancies are dominant, oxide precipitates easily occur in the region.

(11) From a correlation between these BMD density and RTA temperature, a relational equation of BMD density and RTA temperature is then formulated.

(12) In this event, the silicon single crystal wafer preferably has an oxygen concentration of 13 ppma (JEIDA) or more and less than 17 ppma (JEIDA), the RTA heat treatment is preferably performed for a heat-treatment time of 1 second or more and less than 10 seconds, and the second heat treatment is preferably performed under conditions of 850 to 950° C. and 2 hours or more and less than 32 hours.

(13) Within the ranges of these conditions, a relational equation of BMD density and RTA temperature is suitably achieved.

(14) For example, when the nitriding atmosphere is an ammonia-containing atmosphere (a mixed atmosphere of ammonia and argon), the relational equation of
BMD density (/cm.sup.3)=3×10.sup.40 exp(−8.86 eV/kT)
holds where the RTA temperature is within the range of 1150 to 1250° C. and the BMD density is within the range of 1×10.sup.9 to 1×10.sup.11 per cm.sup.3.

(15) Since this relational equation depends on the heat treatment atmosphere of the RTA, it is necessary to determine in advance a relational equation of BMD density and RTA temperature in the atmosphere of the RTA to be actually performed.

(16) When the RTA temperature is within the range of 1150 to 1250° C., the BMD density becomes higher as the RTA temperature becomes higher. When the RTA temperature is higher than 1250° C., the BMD density shows a constant value or is inclined to decrease somewhat.

(17) This is considered to be because, even when the equilibrium concentration of vacancies V become higher, the form of the precipitate nuclei during an RTA heat treatment process changes from VO.sub.2 to 4VO.sub.2 in a higher temperature range, so that many Vs are consumed for forming precipitate nuclei.

(18) In addition, in the heat treatment of the present invention, BMDs are formed in both a plate form and a polyhedron form, and the size is about 40 to 300 nm (diagonal length) in the case of a plate, and about 10 to 50 nm (diagonal length) in the case of a polyhedron.

(19) In the above, a CW wafer is used for performing the RTA heat treatment in a nitriding atmosphere, and then the second heat treatment is performed after processing into a PW wafer. Nevertheless, when only the relation between the BMD density and the RTA temperature is required, it is possible to use a PW wafer for performing the RTA heat treatment, and then perform the second heat treatment.

(20) Next, using the relational equation of RTA temperature and BMD density formulated in advance, the RTA temperature for achieving a predetermined BMD density is determined, or a BMD density is estimated from the RTA temperature.

(21) For example, when RTA is performed in an ammonia-containing atmosphere, the BMD density to be controlled is set, and the RTA temperature is determined using the relational equation:
BMD density (/cm.sup.3)=3×10.sup.40 exp(−8.86 eV/kT).

(22) When manufacturing an annealed wafer having a predetermined BMD density, a silicon single crystal wafer composed of an Nv region is CW-processed, and RTA heat-treated under an ammonia-containing atmosphere at the temperature determined from the above relational equation for 1 second or more and less than 10 seconds to form oxide precipitate nuclei.

(23) Next, after a nitride film formed on the surface is removed by PW-processing, the second heat treatment is performed at 850 to 950° C. for 2 to 32 hours to grow and stabilize the oxide precipitate nuclei.

(24) The atmosphere in this second heat treatment may be an argon atmosphere or an oxygen atmosphere.

(25) When the atmosphere in the second heat treatment is an oxygen atmosphere, cleaning with hydrofluoric acid or the like is necessary to remove an oxide film formed on the surface.

(26) Furthermore, an epitaxial layer may be formed on the surface of the annealed wafer obtained in this manner to obtain an epitaxial wafer.

EXAMPLE

(27) Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Example, but the present invention is not limited thereto.

Example 1

(28) In Example 1, the following wafers were prepared and heat treatments were performed under the following conditions.

(29) (Silicon Single Crystal Wafers)

(30) Diameter: 300 mm

(31) Defect region: Nv region

(32) Oxygen concentration: 14 ppma, 16.3 ppma (2 levels)

(33) (RTA Conditions)

(34) Temperature: 1125 to 1275° C.

(35) Time: 9 seconds

(36) Atmosphere: NH.sub.3+Ar

(37) (Second Heat Treatment Conditions)

(38) Temperature: 900° C.

(39) Time: 2 hours

(40) Atmosphere: Ar

(41) Polished wafers (PW) and epitaxial wafers (EPW) obtained from the above wafers were subjected to the above heat treatment. Then, a heat treatment for revealing BMDs was performed at 780° C., 3 hours (O.sub.2)+1000° C., 2 hours (3% O.sub.2+97% N.sub.2), and the BMD density was measured by RIE method to determine the correlation between the BMD density and the RTA temperature.

(42) In this event, the EPW used had an epitaxial layer with a thickness of 4 μm.

(43) As a result, it was confirmed that the relational equation of
BMD density (/cm.sup.3)=3×10.sup.40 exp(−8.86 eV/kT)
holds when the RTA temperature is within the range of 1150 to 1250° C. FIG. 1 shows this correlating equation.

(44) In the figure, RTA_ANN shows the heat treatment conditions of RTA+900° C./2 hrs on the PW, and RTA_ANN_EP shows the heat treatment conditions of RTA+900° C./2 hrs+4 μm EP on the EPW.

(45) Next, to form BMDs with a density of 1.0×10.sup.10/cm.sup.3 in a silicon single crystal wafer with a diameter of 300 mm, a defect region of Nv region, and an oxygen concentration of 14 ppma, the RTA temperature was set to 1198° C. using the relational equation between the RTA temperature and the BMD density formulated in the above.

(46) Next, a different wafer with the same quality as those used above was CW-processed, then an RTA heat treatment was performed with NH.sub.3+Ar atmosphere, 1198° C., and 9 seconds, and then a PW-process was performed.

(47) Next, a second heat treatment was performed under the conditions of Ar atmosphere, 900° C., and 2 hours.

(48) Then, a heat treatment for revealing BMDs was performed at 780° C., 3 hours (O.sub.2)+1000° C., 2 hours (3% O.sub.2+97% N.sub.2), and the BMD density was measured by RIE method. As a result, the BMD density was 1.02×10.sup.10/cm.sup.3, and the target BMD density was achieved.

Example 2

(49) In Example 2, the following wafers were prepared and heat treatments were performed under the following conditions.

(50) (Silicon Single Crystal Wafers)

(51) Diameter: 300 mm

(52) Defect region: Nv region

(53) Oxygen concentration: 14 ppma

(54) (RTA Conditions)

(55) Temperature: 1200° C.

(56) Time: 9 seconds

(57) Atmosphere: NH.sub.3+Ar

(58) (Second Heat Treatment Conditions)

(59) Temperature: 800 to 1000° C.

(60) Time: 2 hours

(61) Atmosphere: Ar

(62) After performing the above heat treatment, a heat treatment for revealing BMDs was performed at 780° C., 3 hours (O.sub.2)+1000° C., 2 hours (3% O.sub.2+97% N.sub.2), and the BMD density was measured by RIE method.

(63) Since the BMD density determined from the correlating equation of the present invention was 1.13×10.sup.10/cm.sup.3, it was confirmed that the correlating equation between the RTA temperature and the BMD density holds when the second heat treatment is within the range of 850 to 950° C. The results are shown in FIG. 2.

Comparative Example 1

(64) Except that the RTA temperature was set to 1100° C., the BMD density was measured under the same conditions as in Example 1 using a silicon single crystal wafer having the same quality as that of Example 1, that is, a diameter of 300 mm, a defect region of Nv region, and an oxygen concentration of 14 ppma, in order to control the BMD density to 1.0×10.sup.10/cm.sup.3 as in Example 1.

(65) As a result, the BMD density was 1.1×10.sup.9/cm.sup.3, and the result deviated significantly from the target value.

(66) It should be noted that the present invention is not limited to the above-described embodiments. The embodiments are just examples, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept disclosed in claims of the present invention are included in the technical scope of the present invention.