WO2004003265A1 - シリコン単結晶材料とその製造方法 - Google Patents
シリコン単結晶材料とその製造方法 Download PDFInfo
- Publication number
- WO2004003265A1 WO2004003265A1 PCT/JP2002/006654 JP0206654W WO2004003265A1 WO 2004003265 A1 WO2004003265 A1 WO 2004003265A1 JP 0206654 W JP0206654 W JP 0206654W WO 2004003265 A1 WO2004003265 A1 WO 2004003265A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- temperature
- cooling
- sec
- single crystal
- silicon single
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/14—Heating of the melt or the crystallised materials
Definitions
- the present invention relates to a silicon single crystal material by the CZ method, which is different from a semiconductor silicon wafer and has a required thickness such as a thick plate or a block material and is used for an electrode or a part of a semiconductor manufacturing apparatus or the like.
- Silicon which is a single crystal material having a specific resistance within ⁇ 10% of the specific resistance value specified from the sample grown by the CZ method and having a resistance of 10 ⁇ 'cm or more, in which the thermal donor is erased and cracks are not generated.
- the present invention relates to a single crystal material and a method for producing the same. Background art
- Silicon single crystals are widely used not only as semiconductor wafers but also as electrode support materials used in various semiconductor manufacturing equipment. Oxygen is mixed into the silicon single crystal due to contamination from the quartz melted during the pulling by the CZ method, and the oxygen concentration in the crystal is approximately 1 ⁇ 10 18 atoms / cc.
- This oxygen concentration is necessary for the purpose of gettering metal contaminants in the process when used for semiconductor wafers and the like and for maintaining the strength of the wafer. It is controlled within the concentration range.
- the resistivity decreases.
- P-type when the number of lisa-mal donors is larger than the dopant concentration, the type is inverted to N-type, and the specific resistance may decrease in some cases.
- the effective carrier concentration C can be expressed by the following equation, where P, N, and the concentrations of the thermal donor are CP, Cn, and Ctd.
- thermal donor when the dopant concentration is sufficiently high with respect to the generated thermal donor concentration Ctd, that is, when the specific resistance is low, thermal donor can be neglected, and it is necessary to perform thermal donor kill treatment.
- the specific resistance is about 1 ⁇ ⁇ ⁇
- the residual concentration or the regenerated donor at the time of thermal donor killer treatment can be ignored.
- the resistivity exceeds ⁇
- the dopant concentration becomes less than several ppba, and the regenerated donor cannot be ignored. Therefore, when the specific resistance exceeds 10 ⁇ ⁇ ⁇ , it is difficult to perform the thermal resonance treatment.
- the silicon single crystal produced by the CZ method has the problem that the specific resistance value fluctuates due to the oxygen content. Need.
- the thickness is less than lmm as in the so-called wafer, there is no problem by applying the conventional quenching method.
- plasma etchers In the case of a single crystal silicon material used for electrodes and other parts, various forms can be obtained with a thickness and shape different from that of wafers.
- the size of the component material is 250 mm in outside diameter and 10 mm in thickness.
- a temperature difference occurs between the inside and the outside, and a thermal donor is generated particularly due to a decrease in the cooling rate inside, and the ratio is low. A shift in resistance occurs.
- Such a silicon single crystal material is used for a sputtering target for semiconductor wiring, an electrode for plasma etching, and the like.However, in such an application, if the specific resistance is out of a target specific resistance, required sputtering etching cannot be performed. Therefore, the specific resistance value is required to be within ⁇ 10% of the target value.
- single crystal silicon has the property that the temperature decreases to around 700 ° C and the rupture stress decreases. This causes problems such as cracks due to the stress generated during cooling, leading to lower yield and lower quality.
- the present invention aims at a silicon single crystal material having a required thickness such as a thick plate or a block material by a CZ method, and having a specific resistance value specified from a sample grown after the CZ method.
- the purpose of the present invention is to provide a method for producing a single-crystal material having a soil content of 10% or less and having a resistivity of 10 ⁇ ⁇ ⁇ or more without erasing the thermal donor and generating no cracks.
- the inventors investigated in detail the relationship between the temperature range of the thermal donor and the relationship between the rupture strength and the thermal stress, and the temperature range was approximately 400 ° C to 550 ° C. Was found to occur when the temperature was below 100 ° C / min.
- the inventors of the present invention have conducted intensive studies on heat treatment in silicon single crystal materials such as thick plates and block materials in which thermal donors can be erased and cracks do not occur.As a result, at least during cooling after heat treatment for erasing thermal donors, Rapid cooling in the range from 550 ° C to 400 ° C, most widely in the range from the pre-heat treatment completion temperature to 350 ° C, and cooling after completion of quenching, for example, from 400 ° C to room temperature, should be slower than the rapid cooling rate. It was found that the measured resistivity value after the heat treatment was within ⁇ 10% of the resistivity value specified from the sample grown by the CZ method, that cracks did not occur, and that the above-mentioned object could be achieved. Completed the invention.
- a method for producing a silicon single crystal material comprising: a cooling step of setting a cooling rate in a range from a quenching completion temperature to room temperature to C / sec or less.
- the specific resistance is 10 ⁇ ⁇ ⁇ or more
- the oxygen concentration is 1 ⁇ 10 17 atoms / cm 3 or more
- the thickness is 5mn!
- Figure 1 is a graph showing the temperature dependence of the thermal expansion coefficient of silicon (Si) .
- the horizontal axis is temperature (° C)
- the left vertical axis is the Si linear thermal expansion coefficient ( ⁇ ⁇ - 6 )
- the right vertical axis is the da / dT (X lO- 9) .
- the inventors have investigated in detail the relationship between the thermal donor generation temperature region and the breaking strength and thermal stress, and found that the thermal donor generation region is approximately
- the inventors focused on dividing the heat treatment into a thermal donor generation region and a temperature region lower than that, and changing the cooling rate to optimize the heat treatment. Invented a first cooling step for rapidly cooling the temperature range from 550 ° C to 400 ° C, and a second cooling step for relatively slow recooling from 400 ° C to room temperature.
- the target silicon single crystal material is a material having a specific resistance of 10 ⁇ ⁇ ⁇ or more and an oxygen concentration of l ⁇ 10 17 atoms / cm 3 or more.
- the target is not a thin silicon wafer, but a material with a thickness of about 5 mm to 50 mm.
- the diameter of the material is not particularly limited, and currently 100 mm or more or 300 mm or more can be obtained, and any size can be adopted.
- the heat treatment step of holding at a temperature of 550 ° C or more and 800 ° C or less for 15 minutes or more is a heat treatment for erasing a thermal donor, and a holding temperature range of less than 550 ° C for a long time.
- the temperature exceeds 800 ° C, the generation of new oxygen precipitates is a concern and the specific resistance may fluctuate.
- ° C to 800 ° C preferably
- the range is from 600 oC to 700 oC .
- the retention time must be at least 15 minutes in order to erase the samuldona, preferably 30 minutes or more.If it exceeds 60 minutes, the effect tends to be saturated, so 60 minutes The following is preferred.
- the method of raising the temperature up to the processing temperature and the rate of temperature increase are not particularly limited.
- the material can be put into a furnace maintained at 600 ° C., but preferably, the material is temporarily heated after being put into the furnace. Good to do.
- the heat treatment atmosphere is not particularly limited, and the treatment can be performed in a normal atmosphere.
- the thermal treatment temperature of 350 ° C to 350 ° C. If the cooling rate is less than 2 ° C / sec, the concentration of thermal donors regenerated during cooling increases, so that the cooling rate is 2 ° C / sec or more, preferably 5 ° C / sec. It should be more than 10 ° C / sec, and more than 10 ° C / sec.However, if it is too fast, it will be 350 ° C or less at a stretch, causing cracks and the like. It may be appropriate to select according to the situation.
- the quenching temperature range is set to 550 ° C to 400 ° C and the thermal donor-killer heat treatment temperature is set to 350 ° C to eliminate the thermal donor and prevent cracks and slips from occurring.
- the thermal donor-killer heat treatment temperature is set to 350 ° C to eliminate the thermal donor and prevent cracks and slips from occurring.
- the core range is from 700 ° C or 650 ° C to 550 ° C.
- the effect of the present invention can be obtained even at a speed lower than the quenching speed.
- the heat treatment temperature is selected in the range of 550 ° C to 800 ° C, and cooling is started after holding for a predetermined time.However, the holding temperature after completion of the heat treatment step is the cooling start temperature of the rapid cooling step. , If the holding temperature is 550 ° C, 550 ° C to 400 ° C, or
- It can be rapidly cooled in the range of 650 ° C to 350 ° C, for example, at a cooling rate of 10 ° C / sec or more.
- the holding temperature is 800 ° C high, after cooling down from the holding temperature to the required temperature, quench at least in the range of 550 ° C to 400 ° C at 2 ° C / sec or more. If it is possible, it is also possible to cool from the holding temperature to 400 ° C or 350 ° C in multiple stages.
- the material to be treated is taken out of the furnace, and kept outside the furnace or cooled down to a predetermined temperature in another cooling furnace, and then blown with compressed air or taken out of the heat treatment furnace
- Various cooling and quenching methods can be adopted, such as blowing compressed air immediately.
- the step of quenching at least the above-mentioned range from 550 ° C to 400 ° C at 2 ° C / sec or more is most important, and the cooling rate in the range from the quenching completion temperature to room temperature is the quenching step.
- a slower cooling step at l ° C / sec or less a true value of the silicon single crystal material of lOQ.cm or more can be obtained, and the occurrence of slip cracks can be prevented.
- the cooling rate in the range from the quenching completion temperature to room temperature is rC / sec (60 ° C / min) or less, not only 0.5 / sec (30 ° C / min) but also l ° C / min or 0.5 ° C Cooling rates as slow as ° C / min can be adopted.
- cooling method from the quenching completion temperature to room temperature after quenching treatment by blowing compressed air, simply leave it to cool, return it to a furnace maintained at about 350 ° C, cool it down, or cool it with a warm furnace. After cooling, it is possible to adopt various methods such as cooling outside the furnace. If the cooling rate is rC / sec (60 ° C / min) or less, it is also possible to adopt a multi-step cooling rate.
- a two-stage cooling process which is the above-described quenching process and a cooling process slower than the quenching process, is adopted.
- the cooling atmosphere is not particularly limited, for example, in the air.
- An inert gas atmosphere is preferable, and in the case of lamp annealing, it is necessary to be in a vacuum.
- a 350mm outer diameter circle consisting of five types of 5mm, 10mm, 20mm, 35mm, and 50mm in thickness, cut out from a silicon single crystal ingotori with an outer diameter of 350mm grown by the CZ method. ) was prepared.
- the specific resistance of the lmm-thick wafer sliced from the silicon single crystal ingot after heat treatment for thermal donor erasure was 32. ⁇ ⁇ ⁇ .
- As a heat treatment for erasing the thermal donor a condition of holding at 650 ° C for 30 minutes was adopted. Using a normal resistance heating furnace, the temperature was raised to 650 ° C after the furnace was inserted at room temperature and held.
- the atmosphere was an argon gas atmosphere.
- the cooling rate is 2 ° C / sec or more in the first cooling step, the compressed air volume is adjusted and injected into the disc member taken out of the heating furnace to cool it. The same applies to the cooling rate of 1 ° C / sec. If the cooling rate is l ° C / sec, if the cooling rate is 0.5 ° C / sec, the atmosphere is adjusted by cooling, and the furnace is used for l ° C / min and 0.5 ° C / min. Was carried out.
- Table 1 shows the measurement and observation results. Table 1 shows the case where the thickness of the disk member is 20 nm, the first cooling rate is 10 ° C / sec, and the second cooling rate is 0.5 ° C / sec.
- the starting temperature of the above primary cooling is set to 600 ° C, 550 ° C, 500 ° C, 450 ° C, and up to 400 ° C or 350 ° C, respectively. Rapid cooling at 400 ° C / sec, then cooling from 400 ° C or 350 ° C to room temperature at rc / min.Measure the specific resistance of each disk member and observe the occurrence of cracks. did.
- the quenching start temperature is 550 ° C, that is, 550 ° C to 400 ° C or
- Example 1 two kinds of disk members (P type, plane orientation [100]) having a thickness of 35 mm and a thickness of 50 mm and an outer diameter of 350 mm were used, and the same resistance heating furnace was used as a heat treatment for eliminating the thermal donor. , At 750 ° C for 30 minutes.
- the mixture was rapidly cooled at a cooling rate of 5 ° C / sec from 750 ° C to 550 ° C and at a rate of 10 ° C / sec from 550 ° C to 350 ° C.
- cooling was performed from 350 ° C to room temperature at a cooling rate of rc / min.
- the specific resistance value of each of the obtained disk members was measured, and the occurrence of cracks and the like was observed.
- a silicon single crystal material by the CZ method having a required thickness such as a thick plate or a block material used for electrodes of a plasma etcher or other parts, etc.
- Characteristics of within ⁇ 10% of the specific resistance value specified from the sample after CZ growth and more than lOQ'cm by a simple method of performing rapid cooling in the temperature range and slower two-stage cooling process This makes it possible to easily obtain an extremely healthy silicon single crystal material which eliminates the thermal donor and does not cause cracks during production or use.
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004517234A JP4105688B2 (ja) | 2002-07-01 | 2002-07-01 | シリコン単結晶材料とその製造方法 |
AU2002311325A AU2002311325A1 (en) | 2002-07-01 | 2002-07-01 | Silicon single crystal material and its production method |
PCT/JP2002/006654 WO2004003265A1 (ja) | 2002-07-01 | 2002-07-01 | シリコン単結晶材料とその製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2002/006654 WO2004003265A1 (ja) | 2002-07-01 | 2002-07-01 | シリコン単結晶材料とその製造方法 |
Publications (1)
Publication Number | Publication Date |
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WO2004003265A1 true WO2004003265A1 (ja) | 2004-01-08 |
Family
ID=29808185
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2002/006654 WO2004003265A1 (ja) | 2002-07-01 | 2002-07-01 | シリコン単結晶材料とその製造方法 |
Country Status (3)
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JP (1) | JP4105688B2 (ja) |
AU (1) | AU2002311325A1 (ja) |
WO (1) | WO2004003265A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018127652A (ja) * | 2017-02-06 | 2018-08-16 | Jx金属株式会社 | 単結晶シリコンスパッタリングターゲット |
JP2018133537A (ja) * | 2017-02-17 | 2018-08-23 | 三菱マテリアル株式会社 | プラズマ処理装置用電極板及びその製造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59190300A (ja) * | 1983-04-08 | 1984-10-29 | Hitachi Ltd | 半導体製造方法および装置 |
EP0391709A2 (en) * | 1989-04-05 | 1990-10-10 | Nippon Steel Corporation | Single silicon crystal sparingly susceptible of stacking fault induced by oxidation and method for production thereof |
JPH05208892A (ja) * | 1992-01-29 | 1993-08-20 | Shin Etsu Handotai Co Ltd | 単結晶シリコン棒の製造方法 |
US5449883A (en) * | 1992-08-07 | 1995-09-12 | Mitsubishi Materials Corporation | Continuous heat treatment system of semiconductor wafers for eliminating thermal donor |
JPH09283495A (ja) * | 1996-04-17 | 1997-10-31 | Sony Corp | 電極および放電発生装置 |
US6086670A (en) * | 1997-12-24 | 2000-07-11 | Sumitomo Sitix Corporation | Silicon wafer and method for producing the same |
-
2002
- 2002-07-01 AU AU2002311325A patent/AU2002311325A1/en not_active Abandoned
- 2002-07-01 JP JP2004517234A patent/JP4105688B2/ja not_active Expired - Fee Related
- 2002-07-01 WO PCT/JP2002/006654 patent/WO2004003265A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59190300A (ja) * | 1983-04-08 | 1984-10-29 | Hitachi Ltd | 半導体製造方法および装置 |
EP0391709A2 (en) * | 1989-04-05 | 1990-10-10 | Nippon Steel Corporation | Single silicon crystal sparingly susceptible of stacking fault induced by oxidation and method for production thereof |
JPH05208892A (ja) * | 1992-01-29 | 1993-08-20 | Shin Etsu Handotai Co Ltd | 単結晶シリコン棒の製造方法 |
US5449883A (en) * | 1992-08-07 | 1995-09-12 | Mitsubishi Materials Corporation | Continuous heat treatment system of semiconductor wafers for eliminating thermal donor |
JPH09283495A (ja) * | 1996-04-17 | 1997-10-31 | Sony Corp | 電極および放電発生装置 |
US6086670A (en) * | 1997-12-24 | 2000-07-11 | Sumitomo Sitix Corporation | Silicon wafer and method for producing the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018127652A (ja) * | 2017-02-06 | 2018-08-16 | Jx金属株式会社 | 単結晶シリコンスパッタリングターゲット |
JP2018133537A (ja) * | 2017-02-17 | 2018-08-23 | 三菱マテリアル株式会社 | プラズマ処理装置用電極板及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4105688B2 (ja) | 2008-06-25 |
AU2002311325A1 (en) | 2004-01-19 |
JPWO2004003265A1 (ja) | 2005-10-27 |
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