TWI657042B - Silicon nitride powder, release agent for polycrystalline silicon ingot and method for manufacturing polycrystalline silicon ingot - Google Patents

Silicon nitride powder, release agent for polycrystalline silicon ingot and method for manufacturing polycrystalline silicon ingot Download PDF

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TWI657042B
TWI657042B TW106143842A TW106143842A TWI657042B TW I657042 B TWI657042 B TW I657042B TW 106143842 A TW106143842 A TW 106143842A TW 106143842 A TW106143842 A TW 106143842A TW I657042 B TWI657042 B TW I657042B
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silicon nitride
powder
nitride powder
mold
silicon
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TW201829303A (en
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王丸卓司
柴田耕司
山尾猛
山田哲夫
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日商宇部興產股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon

Abstract

本發明之目的在於提供一種氮化矽粉末，其可較佳地用作即便於提高單向凝固時之矽之熔融溫度之情形時，或者即便於延長矽之熔融時間之情形時，多晶矽鑄錠之脫模性亦良好的多晶矽鑄錠之脫模劑。本發明提供一種氮化矽粉末，其特徵在於：比表面積為2m2/g以上且13m2/g以下，β型氮化矽之比率為50質量%以上，β型氮化矽之微晶粒徑DC為150nm以上，比表面積當量徑DBET與DC之比DBET/DC(nm/nm)為3以下，藉由粒度分佈測定而獲得之頻度分佈曲線具有兩個波峰，該等波峰之峰頂處於0.5~2μm之範圍及6~30μm之範圍，且上述峰頂之頻度之比為0.1~1。 An object of the present invention is to provide a silicon nitride powder, which can be preferably used as a polycrystalline silicon ingot even when increasing the melting temperature of silicon during unidirectional solidification or even when extending the melting time of silicon A mold release agent for polycrystalline silicon ingots with good mold releasability. The present invention provides a silicon nitride powder, wherein: a specific surface area 2m 2 / g or more and 13m 2 / g or less, the ratio of β-type silicon nitride of not less than 50 mass%, fine crystal grains of β-type silicon nitride The diameter D C is 150 nm or more, and the specific surface area equivalent diameter D BET to D C ratio D BET / D C (nm / nm) is 3 or less. The frequency distribution curve obtained by the particle size distribution measurement has two peaks. The peak of the peak is in the range of 0.5 ~ 2μm and the range of 6 ~ 30μm, and the ratio of the frequency of the above peaks is 0.1 ~ 1.

Description

氮化矽粉末、多晶矽鑄錠用脫模劑及多晶矽鑄錠之製造方法    Silicon nitride powder, release agent for polycrystalline silicon ingot and method for manufacturing polycrystalline silicon ingot   

本發明係關於一種能夠於鑄模形成對鑄模之密接性及脫模性良好之脫模層之氮化矽粉末，尤其是關於一種適合作為多晶矽鑄錠之脫模劑之氮化矽粉末。 The invention relates to a silicon nitride powder capable of forming a mold release layer with good adhesion and mold releasability to a mold, particularly a silicon nitride powder suitable as a mold release agent for polycrystalline silicon ingots.

太陽電池所使用之多晶矽基板通常係自藉由使用垂直布氏爐，使熔融矽單向凝固而製造之多晶矽鑄錠採集。對多晶矽基板要求高性能化及低成本化，為了應對該要求，重要的是抑制熔融矽之單向凝固時雜質向多晶矽鑄錠之混入、及多晶矽鑄錠之良率之提昇。於藉由垂直布氏法之熔融矽之單向凝固中，使用石英製等之鑄模，為了提高多晶矽鑄錠之良率，對鑄模要求多晶矽鑄錠之脫模性良好，一般使用在內壁(與熔融矽接觸之面)塗佈有包含氮化矽粉末之脫模劑之鑄模。 Polycrystalline silicon substrates used in solar cells are usually collected from polycrystalline silicon ingots produced by unidirectional solidification of molten silicon using a vertical Brinell furnace. High performance and low cost are required for polycrystalline silicon substrates. In order to meet this requirement, it is important to suppress the mixing of impurities into polycrystalline silicon ingots during unidirectional solidification of molten silicon and the improvement of the yield of polycrystalline silicon ingots. In the unidirectional solidification of molten silicon by the vertical Brinell method, a casting mold made of quartz or the like is used. In order to improve the yield of polycrystalline silicon ingots, the molds are required to have good releasability of polycrystalline silicon ingots, and are generally used on the inner wall ( The surface in contact with the molten silicon) is coated with a mold containing a mold release agent containing silicon nitride powder.

垂直布氏爐於其構造上而言，熱自鑄模底面向下方逸出，故而鑄模於上下方向產生較大之溫度梯度，鑄模上部之溫度相對變高。近年來，用於太陽電池基板之多晶矽鑄錠有逐漸大型化之傾向，若提高溫度直至鑄模底部之矽(熔點：1414℃)充分熔融，則根據布氏爐之構造，亦有鑄模上部之溫度成為1500℃以上之高溫的情況。於此種情形時，於溫度較高之鑄模上部，有產生多晶矽鑄錠之脫模性變差，又，脫模層自鑄模剝離而附著於多晶矽鑄錠等問題之情況。因此，對多晶矽鑄錠之脫模層要求即便以較高之溫度、例如1500℃以 上進行單向凝固，多晶矽鑄錠之脫模性、或脫模層對鑄模之密接性亦良好。 In terms of the structure of the vertical Brinell furnace, heat escapes downward from the bottom of the mold, so the mold has a large temperature gradient in the up and down direction, and the temperature at the top of the mold becomes relatively high. In recent years, polycrystalline silicon ingots used in solar cell substrates have a tendency to gradually become larger. If the temperature is raised until the silicon at the bottom of the mold (melting point: 1414 ° C) is sufficiently melted, the temperature at the top of the mold will also be increased according to the structure of the Brinell furnace. It becomes a high temperature above 1500 ° C. In this case, the mold releasability of the polycrystalline silicon ingot deteriorates in the upper part of the mold with a higher temperature, and the mold release layer peels from the mold and adheres to the polycrystalline silicon ingot. Therefore, even if the mold release layer of the polycrystalline silicon ingot is subjected to unidirectional solidification at a higher temperature, for example, 1500 ° C or higher, the mold release property of the polycrystalline silicon ingot or the adhesion of the mold release layer to the mold is also good.

因此種背景，期望開發一種氮化矽粉末，其能夠形成即便為了提昇可應用於太陽電池之基板之多晶矽鑄錠之良率而提高單向凝固時之矽之熔融溫度，多晶矽鑄錠之脫模性及對鑄模之密接性亦良好的脫模層。又，若為了獲得長條之多晶矽鑄錠，而使用於上下方向尺寸較大之鑄模，則鑄模上部尤其長時間暴露於高溫，故而期望開發一種氮化矽粉末，其能夠形成即便單向凝固時之矽之熔融時間較長，多晶矽鑄錠之脫模性及對鑄模之密接性亦良好之脫模層。 In view of this background, it is desirable to develop a silicon nitride powder that can form the mold release of the polycrystalline silicon ingot even if the melting temperature of the silicon during unidirectional solidification is increased in order to improve the yield of the polycrystalline silicon ingot applicable to the substrate of the solar cell The mold release layer has good properties and good adhesion to the mold. In addition, if a long polycrystalline silicon ingot is used in a mold with a large vertical dimension, the upper part of the mold is exposed to high temperatures for a long time, so it is desirable to develop a silicon nitride powder that can be formed even when unidirectionally solidified. The silicon has a long melting time, and the mold release layer of the polycrystalline silicon ingot has good mold releasability and good adhesion to the mold.

例如於專利文獻1中記載有如下氮化矽粉末於用作多晶矽鑄錠之脫模劑之情形時，改善塗佈時之作業性，抑制脫模劑之剝離，藉此可降低雜質向多晶矽鑄錠之混入，上述氮化矽粉末係藉由雷射繞射散射法測得之90%粒徑為3.0~10μm、α相之比率為20~60%、鐵之含量為100ppm以下者，粒度分佈具有2個極大值，一個為0.2μm以上且未達1.0μm(極大值1)，另一個為1.0μm以上且8.0μm以下(極大值2)，且極大值1與2之各頻度之比率{(極大值2之頻度)/(極大值1之頻度)}為1.0~5.0，極大值1與2之間隔為0.8~7.8μm。 For example, Patent Document 1 describes that when silicon nitride powder is used as a mold release agent for polycrystalline silicon ingots, the workability during coating is improved, and the release of the mold release agent is suppressed, thereby reducing impurities cast into polycrystalline silicon Incorporation of ingots, the above silicon nitride powder is measured by laser diffraction scattering method with 90% particle size of 3.0 ~ 10μm, α phase ratio of 20 ~ 60%, iron content of 100ppm or less, particle size distribution It has 2 maximum values, one is more than 0.2μm and less than 1.0μm (maximum value 1), the other is 1.0μm and more than 8.0μm (maximum value 2), and the ratio of each frequency of the maximum value 1 and 2 { (Frequency of maximum 2) / (Frequency of maximum 1)} is 1.0 ~ 5.0, and the interval between maximum 1 and 2 is 0.8 ~ 7.8μm.

又，於專利文獻2中記載有如下氮化矽系脫模層具有強度(可避免剝離或者成為薄片而脫落)，機械耐磨耗性優異，上述氮化矽系脫模層係形成於用於多晶矽鑄錠之凝固之坩堝的脫模層，且包含1μm以下之粒子、及2μm~50μm之範圍、較佳為2μm~5μm之範圍之粒子。 In addition, Patent Document 2 describes that the following silicon nitride-based mold release layer has strength (avoids peeling or peeling off as a thin sheet), and is excellent in mechanical wear resistance. The above-mentioned silicon nitride-based mold release layer is formed for The release layer of the solidified crucible of the polycrystalline silicon ingot contains particles below 1 μm and particles in the range of 2 μm to 50 μm, preferably in the range of 2 μm to 5 μm.

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2014-9111號公報 [Patent Document 1] Japanese Patent Application Publication No. 2014-9111

[專利文獻2]日本特表2009-510387號公報 [Patent Document 2] Japanese Special Publication No. 2009-510387

於專利文獻1中記載有如下效果：於α相之比率處於特定之範圍之情形時，藉由粒度分佈測定而獲得之頻度分佈曲線具有兩個波峰，該等波峰之峰頂處於特定之範圍之氮化矽粉末可抑制脫模劑之剝離，降低雜質向多晶矽鑄錠之混入，但亦揭示若粒徑較大之峰頂大於8.0μm，則不存在該效果。又，未對氮化矽之微晶粒徑或與其BET粒徑之比等進行記載，亦未對提高矽之熔融溫度或者延長矽之熔融時間等之情形時多晶矽鑄錠之脫模性或脫模層對鑄模之密接性進行記載。 The following effect is described in Patent Document 1: When the ratio of the α phase is within a specific range, the frequency distribution curve obtained by particle size distribution measurement has two peaks, and the peaks of these peaks are within a specific range Silicon nitride powder can suppress the peeling of the release agent and reduce the mixing of impurities into the polycrystalline silicon ingot, but it also reveals that if the peak size of the larger particle size is greater than 8.0 μm, this effect does not exist. In addition, there is no description of the crystallite size of silicon nitride or the ratio of its BET particle size, etc., nor does it release or release the polycrystalline silicon ingot when the melting temperature of silicon is increased or the melting time of silicon is extended. The mold layer describes the adhesion of the mold.

又，於專利文獻2中記載有於包含1μm以下之粒子、及大於其之2μm~50μm之粒子之情形時，成為不易剝離之脫模層，但較大之粒子之範圍僅記載有大於較小之粒子之廣泛範圍，不僅未具體揭示併用兩種大小之粒子之情形時之效果，且作為較大之粒子之較佳之範圍，亦只不過設為2μm~5μm。又，未對氮化矽之微晶粒徑或與其BET粒徑之比等進行記載，亦未對提高矽之熔融溫度或者延長矽之熔融時間等之情形時多晶矽鑄錠之脫模性或脫模層對鑄模之密接性進行記載。 In addition, Patent Document 2 describes that when particles of 1 μm or less and particles larger than 2 μm to 50 μm are included, it becomes a release layer that is not easily peeled off, but the range of larger particles only describes that it is larger than smaller The wide range of particles not only does not specifically disclose the effect of the case of using particles of two sizes in combination, but also the preferred range for larger particles is only 2 μm to 5 μm. In addition, there is no description of the crystallite size of silicon nitride or the ratio of its BET particle size, etc., nor does it release or release the polycrystalline silicon ingot when the melting temperature of silicon is increased or the melting time of silicon is extended. The mold layer describes the adhesion of the mold.

因此，本發明之目的在於提供一種氮化矽粉末，其可較佳地用作即便於提高單向凝固時之矽之熔融溫度之情形時，或者即便於延長矽之熔融時間之情形時，多晶矽鑄錠之脫模性亦良好的多晶矽鑄錠之脫模劑。 Therefore, the object of the present invention is to provide a silicon nitride powder that can be preferably used even when the melting temperature of silicon during unidirectional solidification is increased, or even when the melting time of silicon is extended, polycrystalline silicon Mold release agent for polycrystalline silicon ingots with good mold releasability.

本發明者等人為了解決上述課題而反覆進行努力研究，發現若使用具有特定之比表面積、特定之β型氮化矽之比率、特定之微晶粒徑及其與比表面積當量徑之比，且具有特定之粒度分佈、尤其是頻度分佈曲線具有兩個波峰，較大之波峰之峰頂處於較大之範圍的氮化矽粉末形成多晶矽鑄錠鑄造用鑄模之脫模層，則即便提高單向凝固時之矽之熔融溫度，多晶矽鑄錠之脫模性、及脫 模層對鑄模之密接性亦良好，從而完成本發明。即，本發明係關於以下之事項。 In order to solve the above-mentioned problems, the present inventors have repeatedly worked hard to find that if a specific surface area, a specific ratio of β-type silicon nitride, a specific crystallite size and a ratio to the equivalent surface area diameter are used, And the specific size distribution, especially the frequency distribution curve has two peaks, the silicon nitride powder with the peak of the larger peak in a larger range forms the release layer of the mold for polycrystalline silicon ingot casting, even if the single The melting temperature of silicon at the time of solidification, the releasability of the polycrystalline silicon ingot, and the adhesion of the release layer to the mold are also good, thus completing the present invention. That is, the present invention relates to the following matters.

(1)一種氮化矽粉末，其藉由BET法測定之比表面積為2m2/g以上且13m2/g以下，β型氮化矽之比率為50質量%以上，於將根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾(Williamson-Hall)式算出之β型氮化矽之微晶粒徑設為DC時，DC為150nm以上，於將根據上述比表面積算出之比表面積當量徑設為DBET時，DBET/DC(nm/nm)為3以下，藉由利用雷射繞射散射法之體積基準之粒度分佈測定而獲得之頻度分佈曲線具有兩個波峰，該等波峰之峰頂處於0.5~2μm之範圍及6~30μm之範圍，且上述峰頂之頻度之比(粒徑0.5~2μm之範圍之峰頂之頻度/粒徑6~30μm之範圍之峰頂之頻度)為0.1~1。 (1) A silicon nitride powder having a specific surface area measured by the BET method of 2m 2 / g or more and 13m 2 / g or less, the ratio of β-type silicon nitride of 50 mass%, according to the type nitrogen β of the silicon powder X-ray diffraction pattern using Williamson - when Hall (Williamson-Hall) calculated by the formula of β-type silicon nitride crystallite diameter set of D C, D C is 150nm or more, according to the above-described When the equivalent surface area of the calculated specific surface area is D BET , D BET / D C (nm / nm) is 3 or less, and the frequency distribution curve obtained by the volume-based particle size distribution measurement by the laser diffraction scattering method There are two peaks, the peaks of these peaks are in the range of 0.5 ~ 2μm and 6 ~ 30μm, and the ratio of the frequency of the above peaks (frequency of peaks in the range of particle size 0.5 ~ 2μm / particle size 6 ~ The frequency of the peak top in the range of 30 μm) is 0.1 to 1.

(2)如上述(1)之氮化矽粉末，其特徵在於：根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾式算出之β型氮化矽之結晶應變為1.5×10-4以下。 (2) The silicon nitride powder as described in (1) above, characterized in that the crystal strain of the β-type silicon nitride calculated by the Williamson-Hall formula based on the powder X-ray diffraction pattern of the β-type silicon nitride is 1.5 × 10 -4 or less.

(3)如上述(1)或(2)之氮化矽粉末，其特徵在於：上述峰頂處於0.5~2μm之範圍及9~30μm之範圍。 (3) The silicon nitride powder as described in (1) or (2) above, characterized in that the peak top is in the range of 0.5-2 μm and 9-30 μm.

(4)如上述(1)至(3)中任一項之氮化矽粉末，其特徵在於：β型氮化矽之比率為70質量%以上。 (4) The silicon nitride powder according to any one of (1) to (3) above, characterized in that the ratio of β-type silicon nitride is 70% by mass or more.

(5)如上述(1)至(4)中任一項之氮化矽粉末，其特徵在於：上述比表面積為2m2/g以上且10m2/g以下。 (5) The silicon nitride powder according to any one of (1) to (4) above, wherein the specific surface area is 2 m 2 / g or more and 10 m 2 / g or less.

(6)如上述(1)至(5)中任一項之氮化矽粉末，其特徵在於：Fe之含有比率為100ppm以下，Al之含有比率為100ppm以下，Fe及Al以外之金屬雜質之含有比率之合計為100ppm以下。 (6) The silicon nitride powder according to any one of (1) to (5) above, characterized in that the Fe content ratio is 100 ppm or less, the Al content ratio is 100 ppm or less, and the metal impurities other than Fe and Al The total content ratio is 100 ppm or less.

(7)一種多晶矽鑄錠用脫模劑，其包含上述(1)至(6)中任一項之氮化矽粉末。 (7) A mold release agent for polycrystalline silicon ingots, comprising the silicon nitride powder according to any one of (1) to (6) above.

(8)一種多晶矽鑄錠之製造方法，其使收容於鑄模內之熔融矽 凝固，其特徵在於：將在與上述熔融矽之接觸面塗佈有如上述(1)至(6)中任一項之氮化矽粉末之鑄模用作上述鑄模。 (8) A method of manufacturing a polycrystalline silicon ingot, which solidifies molten silicon contained in a casting mold, characterized in that the contact surface with the molten silicon is coated with any one of (1) to (6) above The mold of silicon nitride powder is used as the mold.

根據本發明之氮化矽粉末，可提供一種適合作為多晶矽鑄錠之脫模劑之氮化矽粉末，其即便提高單向凝固時之矽之熔融溫度或者延長矽之熔融時間，亦可提昇多晶矽鑄錠之脫模性及脫模層對鑄模之密接性。 According to the silicon nitride powder of the present invention, a silicon nitride powder suitable as a mold release agent for polycrystalline silicon ingots can be provided. Even if the melting temperature of silicon during unidirectional solidification is increased or the melting time of silicon is extended, the polycrystalline silicon can also be improved The release properties of the ingot and the adhesion of the release layer to the mold.

1‧‧‧燃燒合成反應裝置 1‧‧‧Combustion synthesis reaction device

2‧‧‧混合原料粉末 2‧‧‧mixed raw material powder

3‧‧‧石墨製容器 3‧‧‧Graphite container

4‧‧‧點火劑 4‧‧‧Ignition agent

5‧‧‧碳加熱器 5‧‧‧Carbon heater

6‧‧‧耐壓性容器 6‧‧‧Pressure resistant container

7‧‧‧真空泵 7‧‧‧Vacuum pump

8‧‧‧氮氣瓶 8‧‧‧ Nitrogen bottle

9‧‧‧視窗 9‧‧‧window

圖1係實施例1~11及比較例1~3以及比較例6~13之氮化矽粉末之製造所使用之燃燒合成反應裝置的示意圖。 FIG. 1 is a schematic diagram of a combustion synthesis reaction device used in the manufacture of silicon nitride powders of Examples 1 to 11 and Comparative Examples 1 to 3 and Comparative Examples 6 to 13.

對本發明之氮化矽粉末之實施形態詳細地進行說明。 The embodiment of the silicon nitride powder of the present invention will be described in detail.

(氮化矽粉末) (Silicon nitride powder)

本發明之氮化矽粉末之特徵在於：藉由BET法測定之比表面積為2m2/g以上且13m2/g以下，β型氮化矽之比率為50質量%以上，於將根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾式算出之β型氮化矽之微晶粒徑設為DC時，DC為150nm以上，於將根據上述比表面積算出之比表面積當量徑設為DBET時，DBET/DC(nm/nm)為3以下，藉由利用雷射繞射散射法之體積基準之粒度分佈測定而獲得之頻度分佈曲線具有兩個波峰，該等波峰之峰頂處於0.5~2μm之範圍及6~30μm之範圍，且(粒徑0.5~2μm之範圍之峰頂之頻度/粒徑6~30μm之範圍之峰頂之頻度)為0.1~1。上述峰頂之頻度之比亦可為未達1.0、0.95以下、0.9以下、0.8以下、0.7以下、0.6以下。 Silicon nitride of the present invention is characterized in that powder: specific surface area measurement by the BET method of 2m 2 / g or more and 13m 2 / g or less, the ratio of β-type silicon nitride of 50 mass%, according to the type β the silicon nitride powder X-ray diffraction pattern using the Williamson - Hall when calculating the crystallite diameter set of β-type silicon nitride D C, D C is 150nm or more, according to the ratio of the calculated surface area frequency distribution curve of the specific surface area equivalent to the diameter D BET, D BET / D C (nm / nm) is 3 or less, on a volume basis was obtained by using the laser diffraction scattering particle size distribution measurement of the two peaks having , The peaks of the peaks are in the range of 0.5 ~ 2μm and the range of 6 ~ 30μm, and (the frequency of the peaks in the range of particle size 0.5 ~ 2μm / frequency of the peaks in the range of particle size 6-30μm) is 0.1 ~ 1. The ratio of the frequency of the peaks may be less than 1.0, 0.95 or less, 0.9 or less, 0.8 or less, 0.7 or less, or 0.6 or less.

本發明之氮化矽粉末之藉由BET法測定之比表面積為2m2/g以上且13m2/g以下。若比表面積為該範圍，則可形成對鑄模之密接性良好之脫模層。就該觀點而言，比表面積進而較佳為2m2/g以上且10m2/g以下。氮化矽粉末之藉由BET法測定之比表面積亦可為8m2/g以下、6m2/g以下、4m2/g以下。 The silicon nitride powder of the present invention has a specific surface area measured by the BET method of 2 m 2 / g or more and 13 m 2 / g or less. If the specific surface area is in this range, a mold release layer with good adhesion to the mold can be formed. From this viewpoint, the specific surface area is more preferably 2 m 2 / g or more and 10 m 2 / g or less. The silicon nitride powder by the specific surface area measured by BET method may also be 8m 2 / g or less, 6m 2 / g or less, 4m 2 / g or less.

本發明之氮化矽粉末之β型氮化矽之比率為50質量%以上。若β型氮化矽之比率為該範圍，則可形成多晶矽鑄錠之脫模性及對鑄模之密接性均良好之脫模層。就該觀點而言，β型氮化矽之比率進而較佳為大於70質量%。β型氮化矽之比率亦可為60質量%以上、80質量%以上、90質量%以上、95質量%以上，亦可為100質量%。 The ratio of β-type silicon nitride of the silicon nitride powder of the present invention is 50% by mass or more. If the ratio of β-type silicon nitride is within this range, a mold release layer with good mold releasability and adhesion to the mold can be formed. From this viewpoint, the ratio of β-type silicon nitride is preferably more than 70% by mass. The ratio of β-type silicon nitride may be 60% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

氮化矽以外之成分較佳為未達3質量%，進而較佳為未達1質量%，尤佳為未達0.1質量%。若存在氮化矽以外之成分，則於如本案發明之提高單向凝固時之矽之熔融溫度之情形時，或者延長矽之熔融時間之情形時，均有無法獲得多晶矽鑄錠之良好之脫模性之虞。 The components other than silicon nitride are preferably less than 3% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.1% by mass. If there is a component other than silicon nitride, in the case of increasing the melting temperature of silicon during unidirectional solidification or extending the melting time of silicon as invented in this case, a good release of polycrystalline silicon ingots cannot be obtained Modality.

於將根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾式算出之β型氮化矽之微晶粒徑設為DC時，本發明之氮化矽粉末之DC為150nm以上。若DC為該範圍，則可形成即便提高矽之熔融溫度或者延長熔融時間，多晶矽鑄錠之脫模性及對鑄模之密接性亦均良好之脫模層。推測藉由將DC設為150nm以上，即便於例如1500℃以上之高溫下與熔融矽長時間接觸，本發明之氮化矽粉末亦可維持結晶之構造穩定性。就該觀點而言，DC較佳為300nm以上，進而較佳為500nm以上。DC亦可為180nm以上、200nm以上、250nm以上、400nm以上。 Williamson in using powder X-ray diffraction pattern in accordance with β-type silicon nitride - A Hall when calculating the crystallite diameter set of β-type silicon nitride D C, silicon nitride powder of the present invention D C is 150 nm or more. If D C this range, can be formed even if the increase of the melting temperature of silicon or the melting time is prolonged, and the releasability of polysilicon ingot always make good adhesion of the release layer of the mold. D C is set to the estimated by 150nm or more, for example, even if the contact time at a high temperature above 1500 deg.] C and the molten silicon, silicon nitride powder of the present invention can maintain the stability of the crystalline structure. In this view, D C is preferably 300nm or more, and further preferably 500nm or more. D C may also be more than 180nm, 200nm or more, 250nm or more, 400nm or more.

本發明之氮化矽粉末於將根據上述比表面積算出之比表面積當量徑設為DBET時，DBET/DC(nm/nm)較佳為3以下。若DBET/DC(nm/nm)為該範圍，則可形成即便進一步提高矽之熔融溫度，多晶矽鑄錠之脫模性及對鑄模之 密接性亦均良好之脫模層。其原因雖不明確，但推測構成氮化矽粉末之氮化矽之一粒子中之微晶之界面之面積較小者可能進一步提高於高溫下與熔融矽長時間接觸之情形時之氮化矽之結晶的構造穩定性。DBET/DC(nm/nm)亦可為2以下、1.8以下、1.5以下。 When silicon nitride powder of the present invention to set the diameter D BET specific surface area equivalent was calculated according to the ratio of the surface area, D BET / D C (nm / nm) is preferably 3 or less. If D BET / D C (nm / nm) is in this range, a mold release layer with good mold releasability and adhesion to the mold can be formed even if the melting temperature of silicon is further increased. Although the reason is not clear, it is speculated that the smaller the area of the interface of the crystallites in one of the particles of silicon nitride constituting the silicon nitride powder may further increase the silicon nitride when exposed to molten silicon at high temperature for a long time The structural stability of the crystal. D BET / D C (nm / nm) may also be 2 or less, 1.8 or less, 1.5 or less.

本發明之氮化矽粉末之藉由利用雷射繞射散射法之體積基準之粒度分佈測定而獲得之頻度分佈曲線具有兩個波峰，該等波峰之峰頂處於0.5~2μm之範圍及6~30μm之範圍，上述峰頂之頻度之比(粒徑0.5~2μm之範圍之峰頂之頻度/粒徑6~30μm之範圍之峰頂之頻度)為0.1~1。若上述頻度分佈曲線具有兩個波峰，且兩個上述峰頂分別處於上述範圍、其頻度之比處於上述範圍，則脫模層變得緻密，多晶矽鑄錠之脫模性及脫模層對鑄模之密接性均提昇。 The frequency distribution curve of the silicon nitride powder of the present invention obtained by the volume-based particle size distribution measurement using the laser diffraction scattering method has two peaks, and the peak tops of these peaks are in the range of 0.5 to 2 μm and 6 to In the range of 30 μm, the ratio of the frequency of the peaks (frequency of the peaks in the range of 0.5 to 2 μm in particle diameter / frequency of the peaks in the range of 6 to 30 μm in diameter) is 0.1 to 1. If the frequency distribution curve has two peaks, and the two peak tops are in the above range, and the frequency ratio is in the above range, the release layer becomes dense, the release properties of the polycrystalline silicon ingot and the release layer on the mold The tightness is improved.

兩個峰頂中，峰頂為0.5~2μm之範圍之粒子具有提高氮化矽粒子彼此之密接性及氮化矽粒子與鑄模之密接性之效果、及形成緻密之脫模層之效果。因此，若峰頂為0.5~2μm之範圍，則可形成脫模性良好之脫模層。另一方面，峰頂為6~30μm之範圍之粒子具有提高脫模層之耐熱性之效果。因此，若峰頂為6~30μm之範圍，則即便以1500℃以上之高溫使矽熔融，亦不存在脫模層之剝離，可形成良好之脫模層。粒徑較小之峰頂亦可為1.5μm以下、1.0μm以下、0.9μm以下。粒徑較大之峰頂亦可為9μm以上、10μm以上、11μm以上、13μm以上、15μm以上，或者亦可為25μm以下、20μm以下。此處，粒徑較小之峰頂之範圍及粒徑較大之峰頂之範圍可為針對各者於上文敘述之各種範圍之任意組合。又，若上述峰頂之頻度之比(粒徑0.5~2μm之範圍之峰頂之頻度/粒徑6~30μm之範圍之峰頂之頻度)為0.1~1，則可使各粒子之效果為最大限度，氮化矽粒子彼此之密接性及氮化矽粒子與鑄模之密接性均良好，又，可形成緻密之脫模層，故而可形成多晶矽鑄錠之脫模性良好之脫模層。上述峰頂之頻度之比(粒徑0.5~2μm之範圍之峰頂之頻度/粒徑6~30μm之範圍之峰頂之頻 度)亦可為未達1.0、0.95以下、0.9以下、0.8以下、0.7以下、0.6以下。粒徑較小之峰頂亦可為0.6μm~1.5μm之範圍，又，粒徑較大之峰頂亦可為11μm~29μm之範圍。 Among the two peaks, particles with a peak top in the range of 0.5 to 2 μm have the effect of improving the adhesion between the silicon nitride particles and the adhesion between the silicon nitride particles and the mold, and the effect of forming a dense release layer. Therefore, if the peak top is in the range of 0.5 to 2 μm, a mold release layer with good mold releasability can be formed. On the other hand, particles with a peak top in the range of 6 to 30 μm have the effect of improving the heat resistance of the release layer. Therefore, if the peak top is in the range of 6 to 30 μm, even if the silicon is melted at a temperature of 1500 ° C. or higher, there is no peeling of the release layer, and a good release layer can be formed. The peak top with a small particle size may be 1.5 μm or less, 1.0 μm or less, or 0.9 μm or less. The peak top with a larger particle size may be 9 μm or more, 10 μm or more, 11 μm or more, 13 μm or more, 15 μm or more, or may be 25 μm or less and 20 μm or less. Here, the range of the peak top with a small particle size and the range of the peak top with a large particle size may be any combination of the various ranges described above for each. Furthermore, if the ratio of the frequency of the peaks (frequency of the peaks in the range of 0.5 to 2 μm / frequency of the peaks in the range of 6 to 30 μm) is 0.1 to 1, the effect of each particle can be To the greatest extent, the adhesion between the silicon nitride particles and the adhesion between the silicon nitride particles and the mold are good, and a dense mold release layer can be formed, so a mold release layer with good mold release properties for the polycrystalline silicon ingot can be formed. The ratio of the frequency of the above peaks (the frequency of the peaks in the range of 0.5 to 2 μm in particle size / the frequency of the peaks in the range of 6 to 30 μm in size) may also be less than 1.0, 0.95 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less. The peak top of the smaller particle size can also be in the range of 0.6 μm to 1.5 μm, and the peak top of the larger particle size can also be in the range of 11 μm to 29 μm.

本發明之氮化矽粉末較佳為根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾式算出之β型氮化矽之結晶應變為1.5×10-4以下。若β型氮化矽之結晶應變為該範圍，則可形成即便提高矽之熔融溫度，多晶矽鑄錠之脫模性及對鑄模之密接性亦均良好之脫模層。推測藉由將上述結晶應變設為1.5×10-4以下，即便於更高溫下與熔融矽長時間接觸，本發明之氮化矽粉末亦可維持結晶之構造穩定性。就該觀點而言，上述結晶應變進而較佳為1.2×10-4以下，尤佳為1.0×10-4以下。β型氮化矽之結晶應變亦可為1.5×10-4以下、1.4×10-4以下、1.2×10-4以下、1.0×10-4以下、0.8×10-4以下、0.7×10-4以下。 The silicon nitride powder of the present invention is preferably a β-type silicon nitride crystal strain calculated according to the powder X-ray diffraction pattern of β-type silicon nitride using the Williamson-Hall formula to 1.5 × 10 -4 or less. If the crystalline strain of the β-type silicon nitride is within this range, a mold release layer having a good mold releasability and adhesion to the mold can be formed even if the melting temperature of silicon is increased. It is speculated that by setting the above-mentioned crystal strain to 1.5 × 10 -4 or less, the silicon nitride powder of the present invention can maintain the structural stability of the crystal even when it is in contact with molten silicon at a higher temperature for a long time. From this viewpoint, the above-mentioned crystal strain is more preferably 1.2 × 10 -4 or less, and particularly preferably 1.0 × 10 -4 or less. Strain β crystal type silicon nitride may also be of 1.5 × 10 -4 or less, 1.4 × 10 -4 or less, 1.2 × 10 -4 or less, 1.0 × 10 -4 or less, 0.8 × 10 -4 or less, 0.7 × 10 - 4 or less.

本發明之氮化矽粉末之Fe之含有比率為100ppm以下。若Fe之含有比率為該範圍，則可抑制Fe向多晶矽鑄錠之混入，故而可應用於太陽電池用途之多晶矽鑄錠之良率變高。Fe之含有比率較佳為50ppm以下、20ppm以下，尤佳為10ppm以下。又，本發明之氮化矽粉末之Al之含有比率為100ppm以下。若Al之含有比率為該範圍，則可抑制Al向多晶矽鑄錠之混入，故而可應用於太陽電池用途之多晶矽鑄錠之良率變高。Al之含有比率較佳為50ppm以下、20ppm以下，尤佳為10ppm以下。又，Fe及Al以外之金屬雜質之含有比率之合計為100ppm以下。若Fe及Al以外之金屬雜質之含有比率為該範圍，則可抑制Fe及Al以外之金屬雜質向多晶矽鑄錠之混入，故而可應用於太陽電池用途之多晶矽鑄錠之良率變高。Fe及Al以外之金屬雜質之含有比率較佳為50ppm以下、20ppm以下，尤佳為10ppm以下。 The content ratio of Fe in the silicon nitride powder of the present invention is 100 ppm or less. If the content ratio of Fe is within this range, the incorporation of Fe into the polycrystalline silicon ingot can be suppressed, so the yield of polycrystalline silicon ingots that can be applied to solar cell applications becomes high. The content ratio of Fe is preferably 50 ppm or less, 20 ppm or less, and particularly preferably 10 ppm or less. In addition, the content ratio of Al in the silicon nitride powder of the present invention is 100 ppm or less. If the content ratio of Al is within this range, the mixing of Al into the polycrystalline silicon ingot can be suppressed, so the yield of polycrystalline silicon ingots that can be applied to solar cell applications becomes high. The content ratio of Al is preferably 50 ppm or less, 20 ppm or less, and particularly preferably 10 ppm or less. In addition, the total content ratio of metal impurities other than Fe and Al is 100 ppm or less. If the content ratio of metal impurities other than Fe and Al is within this range, the mixing of metal impurities other than Fe and Al into the polycrystalline silicon ingot can be suppressed, so the yield of polycrystalline silicon ingots that can be applied to solar cell applications becomes higher. The content ratio of metal impurities other than Fe and Al is preferably 50 ppm or less, 20 ppm or less, and particularly preferably 10 ppm or less.

(多晶矽鑄錠用脫模劑) (Release agent for polycrystalline silicon ingot)

本發明之多晶矽鑄錠用脫模劑包含本發明之氮化矽粉末。本發明之多晶矽 鑄錠用脫模劑只要以本發明之氮化矽粉末為主成分即可，可包含氮化矽以外之成分，亦可僅由本發明之氮化矽粉末所構成。 The release agent for polycrystalline silicon ingots of the present invention contains the silicon nitride powder of the present invention. The mold release agent for polycrystalline silicon ingots of the present invention only needs to contain the silicon nitride powder of the present invention as a main component, may contain components other than silicon nitride, or may be composed only of the silicon nitride powder of the present invention.

(多晶矽鑄錠之製造方法) (Manufacturing method of polycrystalline silicon ingot)

以下，說明本發明之多晶矽鑄錠之製造方法。本發明之多晶矽鑄錠之製造方法使收容於鑄模內之熔融矽凝固(尤其是單向凝固)，其特徵在於：將在與上述熔融矽之接觸面塗佈有本發明之氮化矽粉末之鑄模用作上述鑄模。 Hereinafter, the method for manufacturing the polycrystalline silicon ingot of the present invention will be described. The manufacturing method of the polycrystalline silicon ingot of the present invention solidifies the molten silicon contained in the mold (especially unidirectional solidification), characterized in that the contact surface with the molten silicon is coated with the silicon nitride powder of the present invention The mold is used as the above-mentioned mold.

(氮化矽粉末之製造方法) (Manufacturing method of silicon nitride powder)

以下，說明本發明之氮化矽粉末之製造方法之一例。本發明之氮化矽粉末例如於藉由利用伴隨矽之燃燒反應之自放熱及蔓延現象之燃燒合成法而合成氮化矽的氮化矽之燃燒合成製程中，使用特定之製造條件，具體而言，於原料之矽粉末中以特定之比率混合作為稀釋劑之氮化矽粉末，減少原料之矽粉末及作為稀釋劑之氮化矽粉末之金屬雜質之含有比率，縮小矽粉末與氮化矽粉末之混合物之填充密度，進行燃燒反應而製作抗壓強度較小之燃燒產物，使用粉碎能量較小且金屬雜質不易混入之方法，且調整為特定之粉碎條件而將所獲得之抗壓強度較小之燃燒產物粉碎，藉此可製造具有金屬雜質之含有比率較少、β型氮化矽之含有比率較大、具有本發明中特定之比表面積及粒徑分佈、微晶粒徑較大且結晶應變較小等特徵之氮化矽粉末。以下，具體地說明該製造方法之一例。 Hereinafter, an example of the method for producing silicon nitride powder of the present invention will be described. The silicon nitride powder of the present invention uses specific manufacturing conditions, for example, in the combustion synthesis process of silicon nitride that synthesizes silicon nitride by a combustion synthesis method that uses self-exothermic and propagation phenomena accompanying the combustion reaction of silicon, specifically In other words, mixing the silicon nitride powder as a diluent in the silicon powder of the raw material at a specific ratio to reduce the content ratio of metal impurities in the silicon powder of the raw material and the silicon nitride powder as the diluent, narrowing the silicon powder and silicon nitride The filling density of the powder mixture is combusted to produce a combustion product with a low compressive strength. A method with less crushing energy and metal impurities is not easy to mix, and adjusted to specific crushing conditions to compare the obtained compressive strength The small combustion products are pulverized, whereby the content ratio of metal impurities is small, the content ratio of β-type silicon nitride is large, the specific surface area and particle size distribution specified in the present invention, and the crystallite size are large and Silicon nitride powder with characteristics such as small crystal strain. Hereinafter, an example of the manufacturing method will be specifically described.

<混合原料粉末之製備步驟> <Preparation steps of mixed raw material powder>

首先，將矽粉末與稀釋劑之氮化矽粉末混合，製備混合原料粉末。由於燃燒合成反應成為1800℃以上之高溫，故而有於進行燃燒反應之部分發生矽之熔融、熔接之情況。為了抑制該情況，較佳為於不妨礙燃燒反應之自蔓延之範圍內，於原料粉末中添加氮化矽粉末作為稀釋劑。稀釋劑之添加率通常為10~50質量%(矽：氮化矽之質量比為90：10~50：50)，進而為15~40質量%。又，就調整燃燒合成反應中所獲得之燃燒產物之β型氮化矽之比率方面而言，亦可添 加NH4Cl或NaCl等。該等添加物有藉由顯熱、潛熱及吸熱反應而降低反應溫度之效果。此處，所獲得之混合原料粉末中之Fe之含有比率、Al之含有比率、Fe及Al以外之金屬雜質之含有比率較佳為分別設為100ppm以下、進而50ppm以下、10ppm以下。因此，矽粉末、稀釋劑之氮化矽粉末均較佳為使用金屬雜質之含有比率較少之高純度之粉末。又，原料粉末之混合所使用之混合容器之內表面及混合介質等與原料粉末接觸之部位較佳為Al及Fe等之含有比率較少之非金屬製素材。原料粉末之混合方法並無特別限制，例如於採用球磨機混合之情形時，混合容器之內表面較佳為樹脂製，混合介質之外表面較佳為氮化矽製。又，較佳為將混合原料粉末之體密度設為未達0.5g/cm3。為了使混合原料粉末之體密度未達0.5g/cm3，較佳為使用體密度為0.45g/cm3以下之矽粉末作為原料粉末。若混合原料粉末之體密度未達0.5g/cm3，則容易使下述<燃燒合成反應步驟>中所獲得之塊狀之燃燒產物之抗壓強度為4MPa以下。 First, the silicon powder and the silicon nitride powder of the diluent are mixed to prepare a mixed raw material powder. Since the combustion synthesis reaction becomes a high temperature above 1800 ° C, the melting and fusion of silicon may occur in the part where the combustion reaction occurs. In order to suppress this, it is preferable to add silicon nitride powder as a diluent to the raw material powder within a range that does not hinder the self-propagation of the combustion reaction. The addition rate of the diluent is usually 10-50% by mass (the mass ratio of silicon: silicon nitride is 90: 10-50: 50), and then 15-40% by mass. In addition, in terms of adjusting the ratio of the β-type silicon nitride of the combustion product obtained in the combustion synthesis reaction, NH 4 Cl or NaCl may also be added. These additives have the effect of reducing the reaction temperature through sensible, latent and endothermic reactions. Here, the content ratio of Fe in the obtained mixed raw material powder, the content ratio of Al, and the content ratio of metal impurities other than Fe and Al are preferably 100 ppm or less, further 50 ppm or less, and 10 ppm or less. Therefore, both the silicon powder and the silicon nitride powder of the diluent are preferably high-purity powders with a relatively low content of metal impurities. In addition, the inner surface of the mixing container used for mixing the raw material powder, and the portion where the mixing medium and the like come into contact with the raw material powder are preferably non-metallic materials having a small content ratio of Al, Fe, and the like. The mixing method of the raw material powder is not particularly limited. For example, when mixing with a ball mill, the inner surface of the mixing container is preferably made of resin, and the outer surface of the mixing medium is preferably made of silicon nitride. In addition, it is preferable to set the bulk density of the mixed raw material powder to less than 0.5 g / cm 3 . In order to make the bulk density of the mixed raw material powder less than 0.5 g / cm 3 , it is preferable to use silicon powder with a bulk density of 0.45 g / cm 3 or less as the raw material powder. If the bulk density of the mixed raw material powder does not reach 0.5 g / cm 3 , it is easy to make the compressive strength of the massive combustion product obtained in the following <combustion synthesis reaction step> to 4 MPa or less.

<燃燒合成反應步驟> <Combustion synthesis reaction step>

繼而，使所獲得之混合原料粉末於含氮環境中燃燒，製作由氮化矽所構成之塊狀之燃燒產物。例如，將混合原料粉末與點火劑一起收容於石墨製等之容器中，於燃燒合成反應裝置內，點燃點火劑，藉由點火劑之氮化燃燒熱而開始混合原料粉末中之矽之氮化反應，使該反應自蔓延至矽整體而完成燃燒合成反應，獲得由氮化矽所構成之塊狀之燃燒產物。 Then, the obtained mixed raw material powder is burned in a nitrogen-containing environment to produce a massive combustion product composed of silicon nitride. For example, the mixed raw material powder and the igniting agent are contained in a container made of graphite, etc., in the combustion synthesis reaction device, the igniting agent is ignited, and the nitriding of silicon in the raw material powder is started by the igniting combustion heat of the igniting agent Reaction, so that the reaction spreads to the whole silicon to complete the combustion synthesis reaction to obtain a massive combustion product composed of silicon nitride.

此處，所獲得之燃燒產物較佳為其抗壓強度為4MPa以下。若燃燒產物之抗壓強度為4MPa以下，則即便於下述<燃燒產物之粉碎、分級步驟>中，不進行使金屬雜質之混入變多且使氮化矽粉末之結晶性降低之粉碎能量較大之粉碎，亦容易獲得本發明中特定之比表面積或具有兩個峰頂之粒度分佈之氮化矽粉末。 Here, the obtained combustion product preferably has a compressive strength of 4 MPa or less. If the compressive strength of the combustion product is 4 MPa or less, even in the following <combustion product crushing and classification step>, the crushing energy which does not increase the mixing of metal impurities and reduces the crystallinity of the silicon nitride powder is lower Large crushing can also easily obtain silicon nitride powder with a specific surface area or particle size distribution with two peaks in the present invention.

<燃燒產物之粉碎、分級步驟> <Steps of crushing and classifying combustion products>

繼而，將所獲得之塊狀之燃燒產物粗粉碎。粗粉碎之粉碎手段並無特別限制，較佳為使用Al及Fe等之含有比率較少之硬質之非金屬製素材作為粉碎介質，進而較佳為使用氮化矽製粉碎介質。由於燃燒產物為塊狀，故而有效率的是藉由輥碎機之粉碎，作為輥碎機，較佳為具備氮化矽等陶瓷製輥。 Then, the obtained block-shaped combustion products are roughly crushed. The pulverization means for coarse pulverization is not particularly limited, and it is preferable to use hard non-metallic materials with a small content ratio such as Al and Fe as the pulverization medium, and more preferably to use a pulverization medium made of silicon nitride. Since the products of combustion are massive, it is efficiently crushed by a roller crusher. As the roller crusher, it is preferable to have ceramic rollers such as silicon nitride.

將藉由如上所述之粗粉碎而獲得之氮化矽粉末過篩，去除尤其粗大之粒子等。過篩中使用之篩較佳為Al及Fe等之含有比率較少之非金屬製，較佳為樹脂製。 The silicon nitride powder obtained by coarse crushing as described above is sieved to remove particularly coarse particles. The sieve used for sieving is preferably made of non-metal having a small content ratio of Al and Fe, and is preferably made of resin.

其次，將藉由粗粉碎而獲得之氮化矽粉末微粉碎。微粉碎之手段並無特別限制，較佳為藉由振磨機之粉碎。於進行藉由振磨機之粉碎之情形時，振磨機用罐之內表面及混合介質等與原料粉末接觸之部位較佳為Al及Fe等之含有比率較少之非金屬製素材。罐之內表面較佳為樹脂製，混合介質較佳為氮化矽製。藉由適當調節振磨機之條件(振幅、振動數、粉碎時間)，可調節比表面積、藉由粒度分佈測定而獲得之頻度分佈曲線中之兩個波峰之峰頂、及該等之頻度之比。較佳為於破裂能相對變小之條件、例如振動數或粉碎時間較少之條件下進行微粉碎。 Next, the silicon nitride powder obtained by coarse crushing is finely crushed. The method of micro-grinding is not particularly limited, and it is preferably pulverized by a vibration mill. In the case of pulverization by a vibratory mill, the inner surface of the tank for the vibratory mill and the portion where the mixed medium contacts the raw material powder are preferably non-metallic materials having a small content ratio of Al and Fe. The inner surface of the tank is preferably made of resin, and the mixed medium is preferably made of silicon nitride. By appropriately adjusting the conditions (amplitude, number of vibrations, crushing time) of the vibratory mill, the specific surface area, the peak tops of the two peaks in the frequency distribution curve obtained by the particle size distribution measurement, and the frequency of these can be adjusted ratio. It is preferable to perform fine pulverization under conditions where the rupture energy is relatively small, for example, when the number of vibrations or pulverization time is short.

如上所述，本發明之氮化矽粉末較佳為藉由如下氮化矽粉末之製造方法而製造：該製造方法係將矽粉末與稀釋劑之氮化矽粉末混合，將所獲得之混合原料粉末填充至容器中，藉由利用伴隨燃燒反應之自放熱及蔓延現象之燃燒合成法使上述矽粉末燃燒並將所獲得之燃燒產物粉碎，上述混合原料粉末中，Fe之含有比率、Al之含有比率、以及Fe及Al以外之金屬雜質之含有比率分別為100ppm以下，體密度未達0.5g/cm3；進而較佳為上述燃燒產物之抗壓強度為4MPa以下；尤佳為於上述燃燒產物之粉碎中使用氮化矽製粉碎介質。 As described above, the silicon nitride powder of the present invention is preferably manufactured by the following method for manufacturing silicon nitride powder: the manufacturing method is to mix the silicon powder and the silicon nitride powder of the diluent, and the obtained mixed raw material The powder is filled into the container, and the above-mentioned silicon powder is burned and the obtained combustion product is pulverized by a combustion synthesis method using self-exothermic and propagation phenomena accompanying the combustion reaction. In the above-mentioned mixed raw material powder, the content ratio of Fe and the content of Al The ratio and the content ratio of metal impurities other than Fe and Al are 100 ppm or less, respectively, and the bulk density is not more than 0.5 g / cm 3 ; further preferably, the compressive strength of the above combustion products is 4 MPa or less; For grinding, a silicon nitride grinding medium is used.

<混合平均粒徑不同之粉末之步驟> <Steps for mixing powders with different average particle sizes>

本發明之氮化矽粉末可將燃燒產物粗粉碎，於破裂能相對較小之條件下進 行微粉碎而獲得，亦可將平均粒徑不同之氮化矽粉末進行混合等而獲得。例如，亦可將對燃燒產物進行粗粉碎並進行分級而獲得之氮化矽粉末與經微粉碎之氮化矽粉末、或於微粉碎後進行分級並調節粒度而成之氮化矽粉末進行混合等而獲得。於此情形時，藉由適當調節粗粉碎後之分級之條件、微粉碎之條件及微粉碎後之分級之條件、混合比率等，可調節比表面積、藉由粒度分佈測定而獲得之頻度分佈曲線中之兩個波峰之峰頂、及該等之頻度之比。又，藉由將對燃燒產物進行粗粉碎並進行分級而獲得之氮化矽粉末、於微粉碎後進行分級並調節粒度而成之氮化矽粉末、或於微粉碎後進行分級並調節粒度而成之氮化矽粉末與公知之氮化矽粉末進行混合，亦可調節比表面積、峰頂及該等之頻度之比。 The silicon nitride powder of the present invention can be obtained by coarsely pulverizing combustion products and finely pulverizing under relatively small cracking energy, or by mixing silicon nitride powders having different average particle diameters. For example, the silicon nitride powder obtained by coarsely pulverizing and classifying the combustion product may be mixed with the finely pulverized silicon nitride powder, or the silicon nitride powder obtained by classifying and adjusting the particle size after fine pulverization. Obtained. In this case, by appropriately adjusting the conditions of classification after coarse grinding, conditions of fine grinding and conditions of classification after fine grinding, mixing ratio, etc., the specific surface area can be adjusted and the frequency distribution curve obtained by particle size distribution measurement The peaks of the two peaks in and the ratio of these frequencies. In addition, the silicon nitride powder obtained by coarsely pulverizing and classifying the combustion product, the silicon nitride powder obtained by classifying after fine pulverization and adjusting the particle size, or the classifying and adjusting the particle size after fine pulverization The mixed silicon nitride powder and the known silicon nitride powder are mixed, and the ratio of specific surface area, peak top and frequency of these can also be adjusted.

[實施例] [Example]

以下，列舉具體例，更詳細地說明本發明。 Hereinafter, specific examples will be given to explain the present invention in more detail.

本發明之氮化矽粉末、用作原料粉末之矽粉末、原料混合粉末及燃燒產物之物性測定、以及將本發明之氮化矽粉末應用於鑄模之脫模劑之情形時的多晶矽鑄錠之脫模性之評價係藉由以下之方法進行。 The physical properties of the silicon nitride powder of the present invention, the silicon powder used as the raw material powder, the raw material mixed powder and the combustion product, and the polycrystalline silicon ingot when the silicon nitride powder of the present invention is applied to the mold release agent The evaluation of mold releasability was performed by the following method.

(氮化矽粉末之比表面積之測定方法、及比表面積當量徑DBET之算出方法) (Measurement method of specific surface area of silicon nitride powder, and calculation method of equivalent surface area equivalent diameter D BET )

本發明之氮化矽粉末之比表面積係使用Mountech公司製造之Macsorb，藉由利用氮氣吸附之BET1點法進行測定而求出。 The specific surface area of the silicon nitride powder of the present invention is determined by measuring with BET 1 point method using nitrogen adsorption using Macsorb manufactured by Mountech Corporation.

又，比表面積當量徑DBET係將構成粉末之所有粒子假設為同一直徑之球，根據下述式(1)求出。 In addition, the specific surface area equivalent diameter D BET is calculated based on the following equation (1), assuming that all particles constituting the powder are balls of the same diameter.

DBET=6/(ρs×S)...(1) D BET = 6 / (ρs × S) ... (1)

此處，ρs係氮化矽之真密度(根據α-Si3N4之真密度3186kg/m3、β-Si3N4之真密度3192kg/m3、及α相與β相之比而算出平均真密度，設為真密度)，S係比表面積(m2/g)。 Here, ρs is the true density of silicon nitride (based on the true density of α-Si 3 N 4 3186 kg / m 3 , the true density of β-Si 3 N 4 3192 kg / m 3 , and the ratio of α phase to β phase The average true density was calculated and set to true density), S-based specific surface area (m 2 / g).

(氮化矽粉末之β型氮化矽之比率之測定方法) (Measurement method of β-type silicon nitride ratio of silicon nitride powder)

本發明之氮化矽粉末之β型氮化矽粉末之比率係以如下之方式算出。針對本發明之氮化矽粉末，使用由銅之球管所構成之靶及石墨單色器，於繞射角(2θ)15~80°之範圍內，每0.02°藉由利用X射線檢測器進行步進掃描之定時步進掃描法進行X射線繞射測定。於氮化矽粉末包含氮化矽以外之成分之情形時，藉由將該等成分之波峰與該等成分之標準試樣對應之波峰進行對比，可求出該等成分之比率。於以下之所有實施例及比較例中，根據所獲得之粉末X射線繞射圖案，確認到本發明之氮化矽粉末僅由α型氮化矽及β型氮化矽構成。而且，本發明之氮化矽粉末之β型氮化矽之比率係藉由G.P.Gazzara and D.P.Messier,"Determination of Phase Content of Si3N4 by X-ray Diffraction Analysis",Am.Ceram.Soc.Bull.,56[9]777-80(1977)中所記載之Gazzara & Messier之方法算出。 The ratio of the β-type silicon nitride powder of the silicon nitride powder of the present invention is calculated as follows. For the silicon nitride powder of the present invention, a target composed of a copper ball tube and a graphite monochromator are used, within the range of diffraction angle (2θ) 15 ~ 80 °, by using X-ray detector every 0.02 ° The X-ray diffraction measurement is performed by the timing step scan method which performs step scan. In the case where the silicon nitride powder contains components other than silicon nitride, the ratio of these components can be obtained by comparing the peaks of these components with the peaks corresponding to the standard samples of these components. In all the examples and comparative examples below, it was confirmed from the obtained powder X-ray diffraction pattern that the silicon nitride powder of the present invention is composed of only α-type silicon nitride and β-type silicon nitride. Moreover, the ratio of β-type silicon nitride of the silicon nitride powder of the present invention is by GPGazzara and DPMessier, "Determination of Phase Content of Si 3 N 4 by X-ray Diffraction Analysis", Am. Ceram.Soc.Bull. , 56 [9] 777-80 (1977) described in the Gazzara & Messier method.

(β型氮化矽之微晶粒徑DC及結晶應變之測定方法) (crystallite size D C and the method of measuring crystal strain of β-type silicon nitride)

本發明之氮化矽粉末之β型氮化矽之微晶粒徑DC及結晶應變係以如下之方式進行測定。針對本發明之氮化矽粉末，使用由銅之球管所構成之靶及石墨單色器，於繞射角(2θ)15~80°之範圍內，每0.02°藉由利用X射線檢測器進行步進掃描之定時步進掃描法進行X射線繞射測定。根據所獲得之本發明之氮化矽粉末之X射線繞射圖案，算出β型氮化矽之(101)、(110)、(200)、(201)及(210)面之各積分寬，將上述積分寬代入至下述式(2)之威廉姆森-霍爾式。以下述式(2)中之「2sinθ/λ」作為x軸，以「βcosθ/λ」作為y軸進行繪圖，使用最小平方法，求出根據該威廉姆森-霍爾式所獲得之直線之截距及斜率。然後，根據上述截距算出β型氮化矽之微晶粒徑DC，又，根據上述斜率算出β型氮化矽之結晶應變。 The silicon nitride powder of the present invention, the crystallite diameter D C and β-type silicon nitride crystal strain in the system in such a manner were measured. For the silicon nitride powder of the present invention, a target composed of a copper ball tube and a graphite monochromator are used, within the range of diffraction angle (2θ) 15 ~ 80 °, by using X-ray detector every 0.02 ° The X-ray diffraction measurement is performed by the timing step scan method which performs step scan. Based on the obtained X-ray diffraction pattern of the silicon nitride powder of the present invention, the integral widths of the (101), (110), (200), (201), and (210) planes of β-type silicon nitride are calculated, The above integral width is substituted into the Williamson-Hall formula of the following formula (2). Use "2sinθ / λ" in the following formula (2) as the x-axis and "βcosθ / λ" as the y-axis to plot, using the least squares method, find the straight line obtained according to the Williamson-Hall formula Intercept and slope. Then the calculated intercept of the β-type silicon nitride crystallite size D C in accordance with, and, the β-type crystalline silicon nitride above the slope of the strain was calculated.

βcosθ/λ=η×(2sinθ/λ)+(1/DC)...(2) βcosθ / λ = η × (2sinθ / λ) + (1 / D C ) ... (2)

(β：積分寬(rad)，θ：布拉格角(rad)，η：結晶應變，λ：X射線源之波 長(nm)，DC：微晶粒徑(nm)) (β: integral width (rad), θ: Bragg angle (rad), η: crystal strain, λ: wavelength of X-ray source (nm), D C: crystallite size (nm))

(氮化矽粉末之粒度分佈及峰頂之測定方法) (Measurement method of particle size distribution and peak top of silicon nitride powder)

本發明之氮化矽粉末、本發明中用作原料之矽粉末之粒度分佈係以如下之方式進行測定。將上述粉末投入至六偏磷酸鈉0.2質量%水溶液中，使用安裝有直徑26mm之不鏽鋼製中心錐之超音波均質機，以300W之輸出進行6分鐘分散處理而製備稀溶液作為測定試樣。使用雷射繞射/散射式粒徑分佈測定裝置(日機裝股份有限公司製造之Microtrac MT3000)對測定試樣之粒度分佈進行測定，獲得體積基準之粒度分佈曲線及其資料。根據所獲得之粒度分佈曲線及其資料，求出本發明之氮化矽粉末之峰頂之粒徑及頻度(體積%)。 The particle size distribution of the silicon nitride powder of the present invention and the silicon powder used as a raw material in the present invention are measured as follows. The above powder was put into a 0.2% by mass aqueous solution of sodium hexametaphosphate, and a dilute solution was prepared by using an ultrasonic homogenizer equipped with a stainless steel center cone with a diameter of 26 mm at an output of 300 W for 6 minutes to prepare a dilute solution as a measurement sample. A laser diffraction / scattering particle size distribution measuring device (Microtrac MT3000 manufactured by Nikkiso Co., Ltd.) was used to measure the particle size distribution of the measured sample to obtain a volume-based particle size distribution curve and its data. According to the obtained particle size distribution curve and its data, the particle size and frequency (volume%) of the peak top of the silicon nitride powder of the present invention are determined.

(氮化矽粉末、矽粉末及原料混合粉末之Fe、Al以及Fe及Al以外之金屬雜質之含有比率之測定方法) (Measurement method for the content ratio of Fe, Al, and metal impurities other than Fe and Al in silicon nitride powder, silicon powder, and raw material mixed powder)

本發明之氮化矽粉末、本發明中用作原料之矽粉末及原料混合粉末之Fe及Al、Fe及Al以外之金屬雜質之含有比率係以如下之方式進行測定。於收容了混合有氫氟酸及硝酸而成之溶液之容器中投入上述粉末並栓緊，對該容器照射微波而進行加熱，將氮化矽或矽完全分解，藉由超純水將所獲得之分解液定容而作為試液。使用SII NanoTechnology公司製造之ICP-AES(SPS5100型)，根據檢測到之波長及其發光強度對試液中之Fe、Al以及Fe及Al以外之金屬雜質進行定量，算出Fe、Al以及Fe及Al以外之金屬雜質之含有比率。 The content ratios of the silicon nitride powder of the present invention, the silicon powder used as the raw material in the present invention, and the raw material mixed powder of Fe and Al, and metal impurities other than Fe and Al are measured as follows. Put the above powder into a container containing a solution of mixed hydrofluoric acid and nitric acid and fasten it, irradiate the container with microwave to heat it, completely decompose silicon nitride or silicon, and obtain it by ultrapure water The decomposed liquid is made up to volume and used as the test solution. Using ICP-AES (SPS5100 type) manufactured by SII NanoTechnology, quantify Fe, Al, and metal impurities other than Fe and Al in the test solution based on the detected wavelength and luminous intensity, and calculate Fe, Al, and Fe and Al The content ratio of metal impurities.

(混合原料粉末之體密度之測定方法) (Measurement method of bulk density of mixed raw material powder)

本發明中所獲得之混合原料粉末之體密度係藉由依據JIS R1628「精細陶瓷粉末之體密度測定方法」之方法求出。 The bulk density of the mixed raw material powder obtained in the present invention is obtained by a method according to JIS R1628 "Measurement method of bulk density of fine ceramic powder".

(燃燒產物之抗壓強度之測定方法) (Measurement method of compressive strength of combustion products)

本發明中所獲得之燃燒產物之抗壓強度係以如下之方式進行測定。自燃燒產物切割出5個一邊為10mm之立方體作為測定試樣。使用手動式抗壓強度測定 裝置(Aikoh Engineering股份有限公司製造，MODEL-1334型)測定上述測定試樣之抗壓強度。對載置於基座之測定試樣施加負載而進行壓縮試驗，根據測得之最大負載算出抗壓強度。本發明中所獲得之燃燒產物之抗壓強度係設為5個測定試樣之抗壓強度之平均值。 The compressive strength of the combustion products obtained in the present invention is measured in the following manner. Five cubes with a side of 10 mm were cut out from the combustion products as measurement samples. The compressive strength of the above-mentioned measured sample was measured using a manual compressive strength measuring device (manufactured by Aikoh Engineering Co., Ltd., Model-1334). Apply a load to the measurement sample placed on the base to perform a compression test, and calculate the compressive strength based on the maximum load measured. The compressive strength of the combustion product obtained in the present invention is set to the average value of the compressive strength of 5 measurement samples.

(多晶矽鑄錠之脫模性之評價方法) (Evaluation method of mold release property of polycrystalline silicon ingot)

於本發明中，使用以本發明之氮化矽粉末作為脫模劑進行塗佈所製作之鑄模，進行多晶矽鑄錠之單向凝固實驗，將多晶矽鑄錠自鑄模脫模，以如下之方式評價本發明之氮化矽粉末。將多晶矽鑄錠可自鑄模脫模，且未於多晶矽鑄錠確認到脫模層之附著之情形設為○，將多晶矽鑄錠可自鑄模脫模，但於多晶矽鑄錠確認到脫模層之附著之情形設為△，將多晶矽鑄錠無法自鑄模脫模，或者即便可脫模，亦於多晶矽鑄錠產生裂紋或缺口之情形設為×。 In the present invention, a mold made by coating with the silicon nitride powder of the present invention as a mold release agent is used to perform a unidirectional solidification experiment of a polycrystalline silicon ingot, and the polycrystalline silicon ingot is demolded from the mold and evaluated as follows The silicon nitride powder of the present invention. The case where the polycrystalline silicon ingot can be demolded from the mold and the adhesion of the release layer is not confirmed in the polycrystalline silicon ingot is set to ○, the polycrystalline silicon ingot can be demolded from the mold, but the polycrystalline silicon ingot is confirmed to be in the mold release layer The adhesion state is set to △, and the polycrystalline silicon ingot cannot be demolded from the mold, or even if it can be demolded, it is set to × when the polycrystalline silicon ingot is cracked or notched.

(多晶矽鑄錠中所包含之金屬雜質之測定方法) (Determination of metal impurities contained in polycrystalline silicon ingots)

以如下之方式測定單向凝固實驗中所獲得之多晶矽鑄錠中所包含之Fe、Al以及Fe及Al以外之金屬雜質。將所獲得之多晶矽鑄錠以切斷面與凝固方向平行之方式一分為二，於該切斷面之中心軸上，將距底部1cm上之位置作為測定位置，藉由飛行時間型二次離子質譜法(ULVAC-PHI公司製造(TRIFT V nano TOF型))進行表面分析。將Fe、Al以及Fe及Al以外之金屬雜質之二次質譜之標準化二次離子強度為1×10-4以上之情形設為檢測到，將未達1×10-4之情形設為未檢測到。此處，標準化二次離子強度係將各圖譜之二次離子強度除以檢測之所有圖譜之二次離子強度所獲得者。 The metal impurities other than Fe, Al, and Fe and Al contained in the polycrystalline silicon ingot obtained in the unidirectional solidification experiment were measured in the following manner. The obtained polycrystalline silicon ingot is divided into two in such a way that the cut surface is parallel to the solidification direction. On the central axis of the cut surface, the position 1 cm away from the bottom is used as the measurement position. Ion mass spectrometry (made by ULVAC-PHI (TRIFT V nano TOF type)) was used for surface analysis. The case where the normalized secondary ion intensity of the secondary mass spectrum of Fe, Al, and metal impurities other than Fe and Al is 1 × 10 -4 or more is detected, and the case where it is less than 1 × 10 -4 is regarded as undetected To. Here, the standardized secondary ion intensity is obtained by dividing the secondary ion intensity of each spectrum by the secondary ion intensity of all the spectra detected.

(實施例1-1) (Example 1-1)

於D50為4.0μm、體密度為0.40g/cm3、Fe之含有比率為3ppm、Al之含有比率為4ppm、Fe及Al以外之金屬雜質之含有比率為3ppm之矽粉末中，以氮化矽之添加率成為20質量%(矽：氮化矽之質量比為80：20)之方式添加作為稀釋劑 之氮化矽粉末(宇部興產股份有限公司製造，製品名「SN-E10」(Fe之含有比率：9ppm，Al之含有比率：2ppm，Fe及Al以外之金屬雜質之含有比率：4ppm))，製成原料粉末。將上述原料粉末收容於填充有氮化矽製球且內壁面經胺酯襯裡之尼龍製罐中，使用批次式振磨機，於振動數1200cpm、振幅8mm之條件下混合0.5小時，獲得混合原料粉末。 In silicon powder with D50 of 4.0 μm, bulk density of 0.40 g / cm 3 , Fe content ratio of 3 ppm, Al content ratio of 4 ppm, and Fe and Al metal impurity content ratio of 3 ppm, silicon nitride The addition rate becomes 20% by mass (the mass ratio of silicon: silicon nitride is 80:20) by adding silicon nitride powder (manufactured by Ube Kosei Co., Ltd., product name "SN-E10" (Fe The content ratio: 9 ppm, the content ratio of Al: 2 ppm, and the content ratio of metal impurities other than Fe and Al: 4 ppm), to make a raw material powder. The above raw material powder was contained in a nylon can filled with silicon nitride balls and the inner wall surface was urethane-lined. Using a batch-type vibratory mill, the mixture was mixed for 0.5 hours under the conditions of a vibration number of 1200 cpm and an amplitude of 8 mm to obtain mixing. Raw material powder.

於圖1中示出本實施例中矽之燃燒合成反應所使用之燃燒合成反應裝置1。將混合上述原料粉末所獲得之混合原料粉末2收容於底面為200×400mm、深度為30mm、厚度為10mm之鳥嘴狀之石墨製容器3中。此時，混合原料粉末之體密度為0.45g/cm3。將鈦粉末與碳粉末以鈦：碳為4：1之質量比進行混合並成形，製備燃燒合成反應所使用之點火劑4，將點火劑4載置於混合原料粉末2上。繼而，將收容有混合原料粉末2及點火劑4之石墨製容器3以碳加熱器5位於點火劑4之正上方之方式收容於具備點火劑加熱用碳加熱器5之耐壓性容器6內。 FIG. 1 shows a combustion synthesis reaction device 1 used in the combustion synthesis reaction of silicon in this embodiment. The mixed raw material powder 2 obtained by mixing the raw material powders is housed in a beak-shaped graphite container 3 having a bottom surface of 200 × 400 mm, a depth of 30 mm, and a thickness of 10 mm. At this time, the bulk density of the mixed raw material powder was 0.45 g / cm 3 . The titanium powder and the carbon powder are mixed and shaped with a mass ratio of titanium: carbon of 4: 1, and an igniter 4 used in a combustion synthesis reaction is prepared, and the igniter 4 is placed on the mixed raw material powder 2. Then, the graphite container 3 containing the mixed raw material powder 2 and the igniter 4 is housed in the pressure-resistant container 6 provided with the igniter heating carbon heater 5 so that the carbon heater 5 is located directly above the igniter 4 .

使用真空泵7將耐壓性容器6內除氣後，自氮氣瓶8將氮氣導入至上述反應容器內，將環境壓力設為0.6MPa。其次，對碳加熱器5通電而對點火劑4進行加熱，點燃上述混合原料粉末，開始燃燒合成反應。於燃燒合成反應中，耐壓性容器6之氮氣環境壓力大致固定為0.6MPa。自視窗9觀察耐壓性容器6之內部，結果燃燒合成反應持續約20分鐘後結束。反應結束後，自耐壓性容器6取出石墨製容器3，回收塊狀之燃燒產物。 After degassing the pressure-resistant container 6 using the vacuum pump 7, nitrogen gas was introduced into the reaction container from the nitrogen bottle 8, and the ambient pressure was set to 0.6 MPa. Next, the carbon heater 5 is energized to heat the igniter 4 to ignite the mixed raw material powder to start the combustion synthesis reaction. In the combustion synthesis reaction, the nitrogen ambient pressure of the pressure-resistant container 6 is approximately fixed at 0.6 MPa. Observing the inside of the pressure-resistant container 6 from the window 9, the combustion synthesis reaction continued for about 20 minutes and ended. After the reaction is completed, the graphite container 3 is taken out from the pressure-resistant container 6 and the massive combustion products are recovered.

自所獲得之燃燒產物去除點火劑附近部分，將剩餘部分藉由內表面經胺酯(urethane)塗覆且具備氮化矽製輥之輥碎機進行粗粉碎，藉由網眼為100μm之尼龍製篩進行過篩，回收篩下之粉末。將所獲得之粉末收容於填充有氮化矽製球且內壁面經胺酯襯裡之氧化鋁製罐中，使用批次式振磨機，於振動數1200cpm、振幅8mm之條件下微粉碎0.25小時，獲得實施例1-1之氮化矽粉末。 於藉由批次式振磨機之粉碎時，添加相對於粉末為1質量%之乙醇作為粉碎助劑。 Remove the part near the igniting agent from the obtained combustion products, and coarsely pulverize the remaining part by a roller crusher having an inner surface coated with urethane and equipped with a roller made of silicon nitride, using nylon with a mesh of 100 μm The sieve is sieved to recover the powder under the sieve. The obtained powder was contained in an aluminum oxide can filled with silicon nitride balls and the inner wall surface was lined with urethane. Using a batch-type vibratory mill, it was finely pulverized for 0.25 hours under the conditions of a vibration number of 1200 cpm and an amplitude of 8 mm. To obtain the silicon nitride powder of Example 1-1. When pulverizing by a batch-type vibrating mill, 1% by mass of ethanol relative to the powder is added as a pulverizing aid.

將實施例1-1中之原料粉末所使用之矽粉末及稀釋劑之物性值、混合原料粉末之物性值及燃燒產物之抗壓強度示於表1，又，將氮化矽粉末之物性值示於表2。 The physical property values of the silicon powder and diluent used in the raw material powder in Example 1-1, the physical property values of the mixed raw material powder and the compressive strength of the combustion products are shown in Table 1, and the physical property values of the silicon nitride powder示 于 表 2。 Shown in Table 2.

實施例1-1之氮化矽粉末之作為多晶矽鑄錠鑄造用鑄模之脫模劑之評價係以如下之方式實施。 The evaluation of the silicon nitride powder of Example 1-1 as a mold release agent for polycrystalline silicon ingot casting molds was carried out as follows.

將實施例1-1之氮化矽粉末收容於可栓緊之聚乙烯製容器中，藉由添加水而以氮化矽粉末之混合比成為20質量%之方式製備。於收納有氮化矽粉末及水之容器中投入氮化矽製球並栓緊，使用批次式振磨機，於振幅5mm、振動數1780cpm之條件下混合5分鐘，獲得氮化矽漿料。 The silicon nitride powder of Example 1-1 was housed in a tightly made polyethylene container, and prepared by adding water so that the mixing ratio of the silicon nitride powder became 20% by mass. Put silicon nitride balls in a container containing silicon nitride powder and water and tighten them. Using a batch-type vibratory mill, mix for 5 minutes under the conditions of amplitude 5mm and vibration number 1780cpm to obtain silicon nitride slurry .

將所獲得之實施例1-1之氮化矽漿料噴霧塗佈於預先加溫至90℃、氣孔率為16%、底面為100mm之正方形、深度100mm之石英製坩堝之內表面，繼而，以90℃乾燥15小時。此時之脫模層之厚度為約0.2mm。進而，使用大氣環境爐，於空氣中以1100℃保持3小時而進行加熱處理，獲得將實施例1-1之氮化矽粉末應用於脫模層之多晶矽鑄錠鑄造用鑄模。 The obtained silicon nitride slurry of Example 1-1 was spray coated on the inner surface of a quartz crucible previously heated to 90 ° C., having a porosity of 16%, a square with a bottom surface of 100 mm, and a depth of 100 mm, and then, Dry at 90 ° C for 15 hours. The thickness of the release layer at this time is about 0.2 mm. Furthermore, using an atmosphere furnace, heat treatment was carried out in the air at 1100 ° C for 3 hours to obtain a mold for casting a polycrystalline silicon ingot using the silicon nitride powder of Example 1-1 as a release layer.

於上述鑄模中填充純度為7N、大小為2~5mm之矽顆粒300g，收容於布氏爐中。於大氣壓之氬氣流通下歷時5小時將爐內升溫至1500℃而使矽顆粒熔融。於1500℃保持24小時後，以50mm/h之下拉速度將上述鑄模下拉，藉此使熔融矽單向凝固，進而冷卻至室溫。又，製作另一個實施例1-1之多晶矽鑄錠鑄造用鑄模，使用該鑄模，將保持溫度變更為1550℃，除此以外，藉由與上述單向凝固實驗相同之方法進行單向凝固實驗。 Fill the above mold with 300g of silicon particles with a purity of 7N and a size of 2 to 5mm, and store them in a Buchner furnace. The argon flow at atmospheric pressure was used to heat the furnace to 1500 ° C for 5 hours to melt the silicon particles. After maintaining at 1500 ° C for 24 hours, the above-mentioned casting mold was pulled down at a pull-down speed of 50 mm / h, whereby the molten silicon was unidirectionally solidified, and then cooled to room temperature. In addition, another mold for polycrystalline silicon ingot casting of Example 1-1 was prepared, and the mold was used to change the holding temperature to 1550 ° C. Except for this, a unidirectional solidification experiment was conducted by the same method as the above unidirectional solidification experiment .

將多晶矽鑄錠自取出之上述鑄模脫模，藉由「多晶矽鑄錠鑄造用鑄模之評價方法」中所說明之方法，評價實施例1-1之多晶矽鑄錠鑄造用鑄模及多晶矽鑄錠。將其結果示於表3。 The polycrystalline silicon ingot was demolded from the above-mentioned mold, and the polycrystalline silicon ingot casting mold and polycrystalline silicon ingot of Example 1-1 were evaluated by the method described in “Evaluation Method of Polycrystalline Silicon Ingot Casting Molds”. The results are shown in Table 3.

(實施例1-2~1-6) (Examples 1-2 ~ 1-6)

將實施例1-2~1-6之微粉碎之時間自實施例1-2依序設為0.30小時、1.50小時、2.50小時、4.00小時、6.00小時，除此以外，以與實施例1-1相同之方式獲得實施例1-2~1-6之氮化矽粉末。然後，使用所獲得之各實施例之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法分別製作2個多晶矽鑄錠鑄造用鑄模。於各實施例中，使用該等鑄模，藉由與實施例1-1相同之方法進行與實施例1-1相同之兩種爐內溫度下之單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模。 The time for the fine pulverization of Examples 1-2 to 1-6 was set from Example 1-2 to 0.30 hours, 1.50 hours, 2.50 hours, 4.00 hours, and 6.00 hours, in addition to Example 1, 1 The silicon nitride powders of Examples 1-2 to 1-6 were obtained in the same manner. Then, using the obtained silicon nitride powder of each example as a mold release agent, two polycrystalline silicon ingot casting molds were produced by the same method as in Example 1-1. In each example, using these casting molds, the one-way solidification experiment at the same two furnace temperatures as in Example 1-1 was performed by the same method as in Example 1-1. 1 The same method is used to evaluate the casting mold for polycrystalline silicon ingot casting.

(實施例1-7) (Example 1-7)

將實施例1-4之氮化矽粉末藉由網眼為40μm之尼龍製篩過篩，回收篩下之粉末而獲得實施例1-7之氮化矽粉末。然後，使用所獲得之實施例1-7之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作2個多晶矽鑄錠鑄造用鑄模。使用該等鑄模，藉由與實施例1-1相同之方法進行1500℃及1525℃兩種爐內溫度下之單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模。 The silicon nitride powder of Example 1-4 was sieved through a nylon sieve with a mesh of 40 μm, and the powder under the sieve was recovered to obtain the silicon nitride powder of Example 1-7. Then, using the obtained silicon nitride powder of Example 1-7 as a mold release agent, two polycrystalline silicon ingot casting molds were produced by the same method as in Example 1-1. Using these molds, unidirectional solidification experiments at two furnace temperatures of 1500 ° C and 1525 ° C were performed by the same method as Example 1-1, and polycrystalline silicon ingot casting was evaluated by the same method as Example 1-1 With a mold.

(實施例1-8) (Example 1-8)

於原料粉末中進而添加作為添加劑之氯化銨(和光純藥製造，純度99.9%)12.4質量%(矽及氮化矽之混合粉末與氯化銨之質量比成為87.6：12.4之方式)，除此以外，以與實施例1-3相同之方式製作實施例1-8之氮化矽粉末。然後，使用所獲得之實施例1-8之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作2個多晶矽鑄錠鑄造用鑄模。使用該等鑄模，藉由與實施例1-1相同之方法進行與實施例1-1相同之兩種爐內溫度下之單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模。 Add ammonium chloride (made by Wako Pure Chemicals, purity 99.9%) as an additive to the raw material powder at 12.4% by mass (the mass ratio of the mixed powder of silicon and silicon nitride to ammonium chloride becomes 87.6: 12.4), except Other than that, the silicon nitride powder of Example 1-8 was produced in the same manner as Example 1-3. Then, using the obtained silicon nitride powder of Example 1-8 as a mold release agent, two casting molds for polycrystalline silicon ingot casting were produced in the same manner as in Example 1-1. Using these molds, unidirectional solidification experiments at the same two furnace temperatures as in Example 1-1 were conducted by the same method as in Example 1-1, and polysilicon was evaluated by the same method as in Example 1-1 Casting mold for ingot casting.

(實施例1-9) (Example 1-9)

針對實施例1-2之氮化矽粉末，使用空氣分級機(Nisshin Engineering公司製 造之商品名「Turbo Classifier」)，將分界點設定為2μm而進行分級，獲得粒徑較大之氮化矽粉末及較小之氮化矽粉末。回收粒徑較大之氮化矽粉末，將該氮化矽粉末及市售之氮化矽粉末(宇部興產股份有限公司製造，製品名「SN-E10」(Fe之含有比率：9ppm，Al之含有比率：2ppm，Fe及Al以外之金屬雜質之含有比率：4ppm))以質量比1：1之比率，使用藉由胺酯塗覆內表面之V型混合機混合0.17小時。然後，使用所獲得之實施例1-9之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作2個多晶矽鑄錠鑄造用鑄模。使用該等鑄模，藉由與實施例1-1相同之方法進行與實施例1-1相同之兩種爐內溫度下之單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模。 For the silicon nitride powder of Example 1-2, an air classifier (trade name "Turbo Classifier" manufactured by Nisshin Engineering Co., Ltd.) was used, and the cut-off point was set to 2 μm for classification to obtain silicon nitride powder with a larger particle size. And smaller silicon nitride powder. The silicon nitride powder with a larger particle size is recovered, and the silicon nitride powder and commercially available silicon nitride powder (manufactured by Ube Kosei Co., Ltd., product name "SN-E10" (Fe content ratio: 9ppm, Al The content ratio: 2 ppm, and the content ratio of metal impurities other than Fe and Al: 4 ppm)) At a mass ratio of 1: 1, a V-type mixer coated with an inner surface by urethane was used for mixing for 0.17 hours. Then, using the obtained silicon nitride powder of Example 1-9 as a mold release agent, two casting molds for polycrystalline silicon ingot casting were produced in the same manner as in Example 1-1. Using these molds, unidirectional solidification experiments at the same two furnace temperatures as in Example 1-1 were conducted by the same method as in Example 1-1, and polysilicon was evaluated by the same method as in Example 1-1 Casting mold for ingot casting.

(實施例1-10) (Example 1-10)

於粗粉碎後，使用於接口部具備氮化矽製襯墊之氣流式粉碎機(Nisshin Engineering股份有限公司製造之SJ-1500型)，於必需空氣量3.0m3/分鐘、原料供給速度250g/分鐘左右之條件下進行粉碎，將所獲得之氮化矽粉末及市售之氮化矽粉末(宇部興產股份有限公司製造，製品名「SN-E10」(Fe之含有比率：9ppm，Al之含有比率：2ppm，Fe及Al以外之金屬雜質之含有比率：4ppm))以質量比2：1之比率，使用藉由胺酯塗覆內表面之V型混合機混合0.17小時，獲得實施例1-10之氮化矽粉末。然後，使用所獲得之實施例1-10之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作2個多晶矽鑄錠鑄造用鑄模。使用該等鑄模，藉由與實施例1-1相同之方法進行與實施例1-1相同之兩種爐內溫度下之單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模。 After the coarse pulverization using a jet pulverizer (Nisshin Engineering Co., Ltd. of manufacture SJ-1500 type) in the interface portion includes a liner made of silicon nitride, the amount of air required to 3.0m 3 / min, raw material feed rate 250g / Pulverize the product under the condition of about one minute, and then obtain the silicon nitride powder and the commercially available silicon nitride powder (manufactured by Ube Kosei Co., Ltd., product name "SN-E10" (Fe content ratio: 9ppm, Al Content ratio: 2 ppm, content ratio of metal impurities other than Fe and Al: 4 ppm)) Mixing at a mass ratio of 2: 1 using a V-type mixer coated with urethane for 0.17 hours to obtain Example 1 -10 silicon nitride powder. Then, using the obtained silicon nitride powder of Example 1-10 as a mold release agent, two polycrystalline silicon ingot casting molds were produced by the same method as Example 1-1. Using these molds, unidirectional solidification experiments at the same two furnace temperatures as in Example 1-1 were conducted by the same method as in Example 1-1, and polysilicon was evaluated by the same method as in Example 1-1 Casting mold for ingot casting.

(實施例1-11) (Example 1-11)

於粗粉碎後，使用於接口部具備氮化矽製襯墊之氣流式粉碎機(Nisshin Engineering股份有限公司製造之SJ-1500型)，於必需空氣量3.0m3/分鐘、原料供給速度250g/分鐘左右之條件下進行粉碎，將所獲得之氮化矽粉末及市售之氮化 矽粉末(宇部興產股份有限公司製造，製品名「SN-E10」(Fe之含有比率：9ppm，Al之含有比率：2ppm，Fe及Al以外之金屬雜質之含有比率：4ppm))以質量比1：1之比率，使用藉由胺酯塗覆內表面之V型混合機混合0.17小時，獲得實施例1-11之氮化矽粉末。然後，使用所獲得之實施例1-11之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作2個多晶矽鑄錠鑄造用鑄模。使用該等鑄模，藉由與實施例1-1相同之方法進行與實施例1-7相同之兩種爐內溫度下之單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模。 After the coarse pulverization using a jet pulverizer (Nisshin Engineering Co., Ltd. of manufacture SJ-1500 type) in the interface portion includes a liner made of silicon nitride, the amount of air required to 3.0m 3 / min, raw material feed rate 250g / Pulverize the product under the condition of about one minute, and then obtain the silicon nitride powder and the commercially available silicon nitride powder (manufactured by Ube Kosei Co., Ltd., product name "SN-E10" (Fe content ratio: 9ppm, Al Content ratio: 2 ppm, content ratio of metal impurities other than Fe and Al: 4 ppm)) At a mass ratio of 1: 1, a V-type mixer coated with an inner surface by urethane was used for mixing for 0.17 hours to obtain Example 1. -11 silicon nitride powder. Then, using the obtained silicon nitride powder of Example 1-11 as a mold release agent, two casting molds for polycrystalline silicon ingot casting were produced in the same manner as in Example 1-1. Using these molds, unidirectional solidification experiments at the same two furnace temperatures as in Example 1-7 were conducted by the same method as Example 1-1, and polysilicon was evaluated by the same method as Example 1-1 Casting mold for ingot casting.

(比較例1-1、1-2) (Comparative examples 1-1, 1-2)

於比較例1-1中將微粉碎之時間設為0.16小時，於比較例1-2中將微粉碎之時間設為12.00小時，除此以外，以與實施例1-1相同之方式獲得比較例1-1及1-2之氮化矽粉末。如表2所示，比較例1-1之氮化矽粉末係比表面積較小為1.8m2/g之粉末，比較例1-2之氮化矽粉末係比表面積較大為14.8m2/g之粉末。然後，使用所獲得之各比較例之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。於各比較例中，使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 In Comparative Example 1-1, the time of fine pulverization was set to 0.16 hours, and in Comparative Example 1-2, the time of fine pulverization was set to 12.00 hours, except that the comparison was obtained in the same manner as in Example 1-1. Examples 1-1 and 1-2 silicon nitride powder. As shown in Table 2, the silicon nitride powder of Comparative Example 1-1 is a powder with a smaller specific surface area of 1.8 m 2 / g, and the silicon nitride powder of Comparative Example 1-2 has a larger specific surface area of 14.8 m 2 / g of powder. Then, using the obtained silicon nitride powder of each comparative example as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. In each comparative example, using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-3) (Comparative Example 1-3)

於原料粉末中進而添加作為添加劑之氯化銨(和光純藥製造，純度99.9%)16.7質量%(矽及氮化矽之混合粉末與氯化銨之質量比成為83.3：16.7之方式)，除此以外，以與實施例1-3相同之方式獲得比較例1-3之氮化矽粉末。比較例1-3之氮化矽粉末如表2所示，係β型氮化矽之比率較少為46%之粉末。然後，使用所獲得之比較例1-3之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 Ammonium chloride (made by Wako Pure Chemicals, purity 99.9%) was added to the raw material powder as an additive to 16.7% by mass (the mass ratio of silicon and silicon nitride mixed powder to ammonium chloride became 83.3: 16.7), except Other than that, the silicon nitride powder of Comparative Example 1-3 was obtained in the same manner as in Example 1-3. The silicon nitride powders of Comparative Examples 1-3 are shown in Table 2, and the ratio of β-type silicon nitride powder is less than 46%. Then, using the obtained silicon nitride powder of Comparative Example 1-3 as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. Using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-4、比較例1-5) (Comparative Example 1-4, Comparative Example 1-5)

將D50為2.5μm、體密度為0.26g/cm3、Fe之含有比率為2ppm、Al之含有比率為3ppm、Fe及Al以外之金屬雜質之含有比率為3ppm之矽粉末填充於內徑30mm之模具中，以1500kg/cm2之壓力進行單軸成型，獲得矽粉末之單軸成型體。將上述成型體填充於石墨製容器中，將其收容於批次式氮化爐中，將爐內置換為氮氣環境後，於氮氣環境下，升溫至1450℃，保持3小時。於冷卻至室溫後，取出氮化產物。將所獲得之氮化產物藉由內表面經胺酯塗覆且具備氮化矽製輥之輥碎機進行粗粉碎，藉由網眼為100μm之尼龍製篩進行過篩，回收篩下之粉末。其次，將上述粉末收容於填充有氮化矽球且內表面經胺酯襯裡之氧化鋁製罐中，藉由批次式振磨機，於振動數1200cpm、振幅8mm之條件下進行微粉碎。於比較例1-4中將微粉碎之時間設為0.33小時，於比較例1-5中將微粉碎之時間設為2.00小時，獲得各比較例之氮化矽粉末。藉由非燃燒合成法之直接氮化法獲得之比較例1-4及比較例1-5之氮化矽粉末如表2所示，分別為微晶粒徑DC較小為50nm及45nm、結晶應變較大為2.55×10-4及2.20×10-4、DBET/DC較大為11.0及4.6之粉末。然後，使用所獲得之各比較例之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。於各比較例中，使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 Silicon powder with D50 of 2.5 μm, bulk density of 0.26 g / cm 3 , Fe content ratio of 2 ppm, Al content ratio of 3 ppm, and metal impurities other than Fe and Al content ratio of 3 ppm is filled with an inner diameter of 30 mm In the mold, uniaxial molding is performed at a pressure of 1500 kg / cm 2 to obtain a uniaxial molded body of silicon powder. The molded body was filled in a graphite container, and it was housed in a batch nitriding furnace. After the furnace was replaced with a nitrogen atmosphere, the temperature was raised to 1450 ° C in a nitrogen atmosphere for 3 hours. After cooling to room temperature, the nitriding product was taken out. The obtained nitrided product was coarsely pulverized by a roller crusher with an inner surface coated with urethane and equipped with a roller made of silicon nitride, sieved through a nylon sieve with a mesh of 100 μm, and the powder under the sieve was recovered . Next, the above powder was contained in an aluminum oxide can filled with silicon nitride balls and urethane-lined inner surface, and was finely pulverized by a batch-type vibratory mill under the conditions of a vibration number of 1200 cpm and an amplitude of 8 mm. In Comparative Example 1-4, the time of fine pulverization was set to 0.33 hours, and in Comparative Example 1-5, the time of fine pulverization was set to 2.00 hours, to obtain silicon nitride powder of each comparative example. By direct nitridation non-combustion synthesis method of Comparative Example 1-4 to obtain the silicon nitride powder and Comparative Examples 1-5 As shown in Table 2, respectively, smaller crystallite diameter D C of 50nm and 45nm, large crystal strain was 2.55 × 10 -4 and 2.20 × 10 -4, D BET / D C is larger powder of 11.0 and 4.6. Then, using the obtained silicon nitride powder of each comparative example as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. In each comparative example, using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-6) (Comparative Example 1-6)

針對實施例1-4之氮化矽粉末，使用空氣分級機(Nisshin Engineering公司製造之商品名「Turbo Classifier」)，將分界點設定為1μm而進行分級，獲得粒徑較大之氮化矽粉末及較小之氮化矽粉末。回收粒徑較大之氮化矽粉末而獲得比較例1-6之氮化矽粉末。比較例1-6之氮化矽粉末如表2所示，係粒徑較小之峰頂較大為3.5μm之粉末。然後，使用所獲得之比較例1-6之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 For the silicon nitride powder of Example 1-4, an air classifier (trade name "Turbo Classifier" manufactured by Nisshin Engineering Co., Ltd.) was used, and the cut-off point was set to 1 μm for classification to obtain silicon nitride powder with a larger particle size. And smaller silicon nitride powder. The silicon nitride powder having a larger particle diameter is recovered to obtain the silicon nitride powder of Comparative Examples 1-6. As shown in Table 2, the silicon nitride powder of Comparative Examples 1-6 is a powder with a smaller particle diameter and a larger peak top of 3.5 μm. Then, using the obtained silicon nitride powder of Comparative Example 1-6 as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. Using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-7) (Comparative Example 1-7)

將微粉碎之時間設為0.2小時，除此以外，以與實施例1-1相同之方式獲得氮化矽粉末。針對所獲得之氮化矽粉末，使用空氣分級機(Nisshin Engineering公司製造之商品名「Turbo Classifier」)，將分界點設定為2μm而進行分級，獲得粒徑較大之氮化矽粉末及較小之氮化矽粉末。回收粒徑較大之氮化矽粉末，將該氮化矽粉末及市售之氮化矽粉末(宇部興產股份有限公司製造，製品名「SN-E10」(Fe之含有比率：9ppm，Al之含有比率：2ppm，Fe及Al以外之金屬雜質之含有比率：4ppm))以按質量比計1：1之比率，使用內表面經胺酯塗覆之V型混合機混合0.17小時，獲得比較例1-7之氮化矽粉末。比較例1-7之氮化矽粉末如表2所示，係粒徑較小之峰頂較大為32.3μm之粉末。然後，使用所獲得之比較例1-8之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 Except that the time for fine pulverization was set to 0.2 hours, silicon nitride powder was obtained in the same manner as in Example 1-1. For the obtained silicon nitride powder, an air classifier (trade name "Turbo Classifier" manufactured by Nisshin Engineering) was used, and the cut-off point was set to 2 μm for classification to obtain silicon nitride powder with a larger particle size and smaller Of silicon nitride powder. The silicon nitride powder with a larger particle size is recovered, and the silicon nitride powder and commercially available silicon nitride powder (manufactured by Ube Kosei Co., Ltd., product name "SN-E10" (Fe content ratio: 9ppm, Al The content ratio: 2 ppm, and the content ratio of metal impurities other than Fe and Al: 4 ppm)) At a ratio of 1: 1 by mass ratio, use a V-type mixer whose inner surface is coated with urethane to mix for 0.17 hours to obtain a comparison Examples 1-7 of silicon nitride powder. As shown in Table 2, the silicon nitride powder of Comparative Examples 1-7 is a powder with a smaller particle size and a larger peak top of 32.3 μm. Then, using the obtained silicon nitride powder of Comparative Examples 1-8 as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. Using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-8) (Comparative Example 1-8)

針對實施例1-3之氮化矽粉末，使用空氣分級機(Nisshin Engineering公司製造之商品名「Turbo Classifier」)，將分界點設定為12μm而進行分級，獲得粒徑較大之氮化矽粉末及較小之氮化矽粉末。回收粒徑較小之氮化矽粉末而獲得比較例1-8之氮化矽粉末。比較例1-8之氮化矽粉末如表2所示，係粒徑較小之峰頂之頻度之粒徑與較大之峰頂之頻度之比大為1.54的粉末。然後，使用所獲得之比較例1-8之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 For the silicon nitride powder of Example 1-3, an air classifier (trade name "Turbo Classifier" manufactured by Nisshin Engineering Co., Ltd.) was used, and the cut-off point was set to 12 μm for classification to obtain silicon nitride powder with a larger particle size. And smaller silicon nitride powder. The silicon nitride powder having a smaller particle size is recovered to obtain the silicon nitride powder of Comparative Examples 1-8. As shown in Table 2, the silicon nitride powders of Comparative Examples 1-8 are powders with a ratio of the diameter of the frequency of the peak with a smaller particle diameter to the frequency of the frequency of the larger peak with a larger ratio of 1.54. Then, using the obtained silicon nitride powder of Comparative Examples 1-8 as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. Using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-9) (Comparative Example 1-9)

針對比較例1-8之氮化矽粉末，使用空氣分級機(Nisshin Engineering公司製 造之商品名「Turbo Classifier」)，將分界點設定為2μm而進行分級，獲得粒徑較大之氮化矽粉末及較小之氮化矽粉末。回收粒徑較小之氮化矽粉末而獲得比較例1-9之氮化矽粉末。比較例1-9之氮化矽粉末係粒徑之峰頂為1個之粉末。然後，使用所獲得之比較例1-9之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 For the silicon nitride powders of Comparative Examples 1-8, an air classifier (trade name "Turbo Classifier" manufactured by Nisshin Engineering Co., Ltd.) was used, and the cut-off point was set to 2 μm for classification to obtain silicon nitride powder with a larger particle size. And smaller silicon nitride powder. The silicon nitride powder having a smaller particle size is recovered to obtain the silicon nitride powder of Comparative Examples 1-9. The silicon nitride powders of Comparative Examples 1-9 are powders having one particle size peak. Then, using the obtained silicon nitride powder of Comparative Example 1-9 as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. Using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

(比較例1-10~1-12) (Comparative Examples 1-10 ~ 1-12)

使用表1所示之粉末作為原料矽粉末，除此以外，以與實施例1-4相同之方式獲得比較例1-10~1-12之氮化矽粉末。比較例1-10~1-12之氮化矽粉末係Fe之含量、Al之含量及Fe、Al以外之金屬雜質之含量分別較多為159ppm、140ppm及134ppm的粉末。然後，使用所獲得之比較例1-10~1-12之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法分別製作1個多晶矽鑄錠鑄造用鑄模。於各實施例中，使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 Except for using the powder shown in Table 1 as the raw material silicon powder, the silicon nitride powders of Comparative Examples 1-10 to 1-12 were obtained in the same manner as in Example 1-4. The silicon nitride powders of Comparative Examples 1-10 to 1-12 are powders in which the content of Fe, Al, and metal impurities other than Fe and Al are respectively 159 ppm, 140 ppm, and 134 ppm. Then, using the obtained silicon nitride powders of Comparative Examples 1-10 to 1-12 as a mold release agent, one polycrystalline silicon ingot casting mold was produced in the same manner as in Example 1-1. In each of the examples, the mold was used to evaluate a polycrystalline silicon ingot casting mold and a silicon ingot by the same method as in Example 1-1.

(比較例1-13) (Comparative Example 1-13)

於燃燒產物之粗粉碎中使用具備氧化鋁製輥之輥碎機，於藉由批次式振磨機之微粉碎中使用填充有氧化鋁製球之氧化鋁製罐，除此以外，以與實施例1-4相同之方式製作比較例1-13之氮化矽粉末。比較例1-13之氮化矽粉末係Fe之含量、Al之含量及Fe、Al以外之金屬雜質之含量均較多為240ppm、3700ppm、129ppm之粉末。然後，使用所獲得之比較例1-13之氮化矽粉末作為脫模劑，藉由與實施例1-1相同之方法製作1個多晶矽鑄錠鑄造用鑄模。使用該鑄模，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。 Use a roller crusher equipped with alumina rollers for the coarse crushing of the combustion products, and use an alumina tank filled with alumina balls for the micro crushing by a batch-type vibratory mill. The silicon nitride powder of Comparative Examples 1-13 was prepared in the same manner as in Example 1-4. The silicon nitride powders of Comparative Examples 1-13 are powders in which the Fe content, Al content, and metal impurities other than Fe and Al are all 240 ppm, 3700 ppm, and 129 ppm. Then, using the obtained silicon nitride powder of Comparative Examples 1-13 as a mold release agent, one polycrystalline silicon ingot casting mold was produced by the same method as in Example 1-1. Using this mold, the mold for polycrystalline silicon ingot casting and the silicon ingot were evaluated by the same method as in Example 1-1.

將實施例1-2~1-11及比較例1-1~1-13中之原料粉末所使用之矽粉末、以及添加劑之物性值、混合原料粉末之物性值及上述燃燒產物之抗壓強 度示於表1，又，將氮化矽粉末之物性值示於表2。又，將實施例1-2~1-11及比較例1-1~1-13之多晶矽鑄錠鑄造用鑄模及多晶矽鑄錠之評價結果示於表3。 The physical property values of the silicon powder and additives used in the raw material powders of Examples 1-2 to 1-11 and Comparative Examples 1-1 to 1-13, the physical property values of the mixed raw material powder and the compressive strength of the above-mentioned combustion products It is shown in Table 1, and the physical property value of silicon nitride powder is shown in Table 2. In addition, Table 3 shows the evaluation results of the molds for polycrystalline silicon ingot casting and polycrystalline silicon ingots of Examples 1-2 to 1-11 and Comparative Examples 1-1 to 1-13.

(實施例2-1) (Example 2-1)

藉由以下所述之方法，製作具備包含實施例1-1之氮化矽粉末之脫模層之多晶矽鑄錠鑄造用鑄模，實施多晶矽鑄錠鑄造用鑄模及矽鑄錠之評價。 The polycrystalline silicon ingot casting mold with the mold release layer containing the silicon nitride powder of Example 1-1 was produced by the method described below, and the evaluation of the polycrystalline silicon ingot casting mold and the silicon ingot was performed.

將實施例1-1之氮化矽粉末收容於可密封之聚乙烯製容器中，添加二氧化矽(silica)濃度20質量%之矽溶膠(扶桑化學公司製造，製品名「PL-3」)及水。此時，以按質量比計氮化矽：矽溶膠：水成為20：8：72之方式進行混合。其次，於收容有氮化矽粉末、矽溶膠及水之容器中投入氮化矽製球並密封，使用批次式振磨機，於振幅5mm、振動數1780cpm之條件下混合5分鐘，獲得氮化矽漿料。 The silicon nitride powder of Example 1-1 was contained in a sealable polyethylene container, and a silica sol with a concentration of 20% by mass of silica (manufactured by Fuso Chemical Co., Ltd., product name "PL-3") was added And water. At this time, the mixing is performed in such a manner that the mass ratio of silicon nitride: silica sol: water becomes 20: 8: 72. Next, put silicon nitride balls in a container containing silicon nitride powder, silica sol, and water and seal them. Using a batch-type vibratory mill, mix for 5 minutes under an amplitude of 5 mm and a vibration number of 1780 cpm to obtain nitrogen. Silicone slurry.

將所獲得之實施例2-1之氮化矽漿料噴霧塗佈於預先加溫至90℃、氣孔率為16%、底面為100mm之正方形、深度100mm之石英製坩堝之內表面，繼而，以90℃乾燥15小時，獲得具備包含實施例2-1之氮化矽粉末之脫模層之多晶矽鑄錠鑄造用鑄模。此時之脫模層之厚度為約0.2mm。 The obtained silicon nitride slurry of Example 2-1 was spray-coated on the inner surface of a quartz crucible previously heated to 90 ° C., having a porosity of 16%, a square with a bottom surface of 100 mm, and a depth of 100 mm, and then, After drying at 90 ° C for 15 hours, a mold for casting a polycrystalline silicon ingot having a mold release layer containing the silicon nitride powder of Example 2-1 was obtained. The thickness of the release layer at this time is about 0.2 mm.

使用所獲得之實施例2-1之多晶矽鑄錠鑄造用鑄模，以與實施例1-1相同之方式進行單向凝固實驗，藉由與實施例1-1相同之方法評價實施例2-1之多晶矽鑄錠鑄造用鑄模及矽鑄錠。將其結果示於表4。 Using the obtained mold for polycrystalline silicon ingot casting of Example 2-1, a unidirectional solidification experiment was carried out in the same manner as Example 1-1, and Example 2-1 was evaluated by the same method as Example 1-1 The mold and silicon ingot for polycrystalline silicon ingot casting. The results are shown in Table 4.

(實施例2-2~2-11、比較例2-1~2-13) (Examples 2-2 to 2-11, Comparative Examples 2-1 to 2-13)

使用表4所示之氮化矽粉末，除此以外，藉由與實施例2-1相同之方法製作氮化矽漿料，製造多晶矽鑄錠鑄造用鑄模。使用所獲得之各實施例及各比較例之多晶矽鑄錠鑄造用鑄模，以與實施例1-1相同之方式進行單向凝固實驗，藉由與實施例1-1相同之方法評價多晶矽鑄錠鑄造用鑄模及矽鑄錠。將其結果示於表4。 Except for using silicon nitride powder shown in Table 4, a silicon nitride slurry was produced by the same method as in Example 2-1, and a mold for polycrystalline silicon ingot casting was produced. Using the obtained molds for polycrystalline silicon ingot casting of each Example and each comparative example, a unidirectional solidification experiment was conducted in the same manner as in Example 1-1, and the polycrystalline silicon ingot was evaluated by the same method as in Example 1-1 Foundry molds and silicon ingots. The results are shown in Table 4.

如上所述，可知本發明之氮化矽粉末藉由於塗佈於鑄模後以高溫進行熱處理，能夠實質上單獨於鑄模形成密接性及脫模性良好之脫模層，又，藉由與矽溶膠混合而塗佈於鑄模，即便不進行高溫之熱處理，亦能夠於鑄模形成密接性及脫模性良好之脫模層。 As described above, it can be seen that the silicon nitride powder of the present invention can be applied to a mold to perform heat treatment at a high temperature, so that a mold release layer with good adhesion and mold releasability can be formed substantially alone from the mold. Mixing and applying to a casting mold can form a mold release layer with good adhesion and mold releasability in the casting mold without performing high-temperature heat treatment.

[產業上之可利用性] [Industry availability]

本發明之氮化矽粉末可用作能夠於鑄模形成對鑄模之密接性及脫模性良好之脫模層的脫模劑，尤其可用作能夠以較高之良率採集太陽電池用高品質之矽基板的多晶矽鑄錠之脫模劑。又，本發明之氮化矽粉末由於能夠形成緻密之脫模層且結晶性較高，故而亦可用作於高溫下表現高強度之氮化矽燒結體之原料。 The silicon nitride powder of the present invention can be used as a mold release agent capable of forming a mold release layer with good adhesion to the mold and mold release property in the mold, especially as a high-quality silicon capable of collecting solar cells with a high yield Mold release agent for polycrystalline silicon ingot of substrate. In addition, the silicon nitride powder of the present invention can form a dense release layer and has high crystallinity, so it can also be used as a raw material for a silicon nitride sintered body that exhibits high strength at high temperatures.

Claims (8)

一種氮化矽粉末，其藉由BET法測定之比表面積為2m2/g以上且13m2/g以下，β型氮化矽之比率為50質量%以上，於將根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾(Williamson-Hall)式算出之β型氮化矽之微晶粒徑設為DC時，DC為150nm以上，於將根據上述比表面積算出之比表面積當量徑設為DBET時，DBET/DC(nm/nm)為3以下，藉由利用雷射繞射散射法之體積基準之粒度分佈測定而獲得之頻度分佈曲線具有兩個波峰，該等波峰之峰頂處於0.5~2μm之範圍及6~30μm之範圍，且上述峰頂之頻度之比(粒徑0.5~2μm之範圍之峰頂之頻度/粒徑6~30μm之範圍之峰頂之頻度)為0.1~1。A nitride silicon powder, which is measured by the BET method specific surface area 2m 2 / g or more and 13m 2 / g or less, the ratio of β-type silicon nitride of 50 mass% or more, according to the β-type silicon nitride powder X-ray diffraction pattern using Williamson - when the crystallite size of the β-type silicon nitride Hall (Williamson-Hall) calculated from the formula set D C, D C is 150nm or more, calculated according to the above-described specific surface area frequency distribution curve of the specific surface area is equivalent to the diameter D BET, D BET / D C (nm / nm) is 3 or less, obtained by using a volume basis of the laser diffraction scattering particle size distribution measurement of having two Peaks, the peaks of these peaks are in the range of 0.5 ~ 2μm and 6 ~ 30μm, and the ratio of the frequency of the above peaks (frequency of peaks in the range of particle size 0.5 ~ 2μm / range of particle size 6 ~ 30μm The frequency of the peak) is 0.1 ~ 1. 如申請專利範圍第1項之氮化矽粉末，其中，根據β型氮化矽之粉末X射線繞射圖案使用威廉姆森-霍爾式算出之β型氮化矽之結晶應變為1.5×10-4以下。For example, the silicon nitride powder according to item 1 of the patent application, in which the crystal strain of the β-type silicon nitride calculated by the Williamson-Hall formula based on the powder X-ray diffraction pattern of the β-type silicon nitride is 1.5 × 10 -4 or less. 如申請專利範圍第1或2項之氮化矽粉末，其中，上述峰頂處於0.5~2μm之範圍及9~30μm之範圍。For example, the silicon nitride powder according to item 1 or 2 of the patent application scope, wherein the peaks are in the range of 0.5 ~ 2μm and the range of 9 ~ 30μm. 如申請專利範圍第1或2項之氮化矽粉末，其中，β型氮化矽之比率為70質量%以上。For example, the silicon nitride powder of the first or second patent application, wherein the ratio of β-type silicon nitride is 70% by mass or more. 如申請專利範圍第1或2項之氮化矽粉末，其中，上述比表面積為2m2/g以上且10m2/g以下。For example, the silicon nitride powder according to item 1 or 2 of the patent application, wherein the specific surface area is 2 m 2 / g or more and 10 m 2 / g or less. 如申請專利範圍第1或2項之氮化矽粉末，其中，Fe之含有比率為100ppm以下，Al之含有比率為100ppm以下，且Fe及Al以外之金屬雜質之含有比率之合計為100ppm以下。For example, in the silicon nitride powder of claim 1 or 2, the content ratio of Fe is 100 ppm or less, the content ratio of Al is 100 ppm or less, and the total content ratio of metal impurities other than Fe and Al is 100 ppm or less. 一種多晶矽鑄錠用脫模劑，其包含申請專利範圍第1至6項中任一項之氮化矽粉末。A mold release agent for polycrystalline silicon ingots, which contains the silicon nitride powder according to any one of patent application items 1 to 6. 一種矽鑄錠之製造方法，其使收容於鑄模內之熔融矽凝固，其特徵在於：將在與上述熔融矽之接觸面塗佈有申請專利範圍第1至6項中任一項之氮化矽粉末之鑄模用作上述鑄模。 A method for manufacturing a silicon ingot, which solidifies molten silicon contained in a casting mold, characterized in that the contact surface with the molten silicon is coated with nitride according to any one of items 1 to 6 of the patent application The mold of silicon powder is used as the above mold.
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