CN100354199C - 用于合成半导体金刚石的石墨材料以及由该材料制备的半导体金刚石 - Google Patents

用于合成半导体金刚石的石墨材料以及由该材料制备的半导体金刚石 Download PDF

Info

Publication number
CN100354199C
CN100354199C CNB018239153A CN01823915A CN100354199C CN 100354199 C CN100354199 C CN 100354199C CN B018239153 A CNB018239153 A CN B018239153A CN 01823915 A CN01823915 A CN 01823915A CN 100354199 C CN100354199 C CN 100354199C
Authority
CN
China
Prior art keywords
graphite material
boron
adamantine
semiconductor
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB018239153A
Other languages
English (en)
Other versions
CN1582257A (zh
Inventor
福长修
大久保博
曾我部敏明
东城哲朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Tanso Co Ltd
Original Assignee
Toyo Tanso Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Tanso Co Ltd filed Critical Toyo Tanso Co Ltd
Publication of CN1582257A publication Critical patent/CN1582257A/zh
Application granted granted Critical
Publication of CN100354199C publication Critical patent/CN100354199C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/062—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies characterised by the composition of the materials to be processed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/065—Presses for the formation of diamonds or boronitrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/065—Presses for the formation of diamonds or boronitrides
    • B01J3/067—Presses using a plurality of pressing members working in different directions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
    • B30B11/004—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses involving the use of very high pressures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
    • B30B11/007—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses using a plurality of pressing members working in different directions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B01J2203/0605—Composition of the material to be processed
    • B01J2203/061—Graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B01J2203/065—Composition of the material produced
    • B01J2203/0655—Diamond
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/421—Boron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/427—Diamond
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Abstract

在由高压合成法制备含硼的半导体金刚石时，向旨在转化为半导体金刚石的石墨材料中按使其均匀的方式加入硼或硼化合物，使之致密、高纯度化，降低含氢量。

Description

用于合成半导体金刚石的石墨材料以及由该材料制备的半导体金刚石
技术领域
本发明涉及在由高压合成法合成含有大量硼的半导体金刚石中所使用的用于合成半导体金刚石的石墨材料、以及使用该材料制备的半导体金刚石。
背景技术
目前，工业金刚石的制备大多采用高压合成法。已知通过高压合成法制备工业金刚石时，如果向催化剂金属等中加入硼，则可合成含有硼的金刚石。并已知硼原子与碳原子交换而进入，在价电子带上方(0.37eV)的部位形成受主能级，形成p型半导体。
最近，发现了利用含硼的金刚石所具有的半导体特性应用于各种电极、耐化学品性感应器、导电性磨削砂轮等中的可能性，使得含硼的半导体金刚石有了大量需求。因此需要高效率、高收率地合成含硼的半导体金刚石。
传统的高压合成法有例如日本特公昭59-6808号公报所示的方法，该方法中，向金刚石合成中用作催化剂的金属中一起添加硼和铝，作为熔融金属兼熔融催化剂使用，这样可以使金刚石单晶在金刚石晶种上生长。然后调节加入到催化剂中的硼的加入量，从而调节合成的金刚石中的硼含量。
但是，该方法中，难以通过调节熔融金属兼熔融催化剂中的硼加入量来使硼以高比例含有。并且也难以使硼在金刚石中均匀分布。还难以高收率获得金刚石。
因此，本发明的目的在于提供用于合成半导体金刚石的石墨材料，该用于合成半导体金刚石的石墨材料可以以高收率制备高比例含有硼或硼化合物、且这些硼或硼化合物均匀分布的半导体金刚石；还提供使用这些材料制备的半导体金刚石。
发明内容
为解决上述问题，本发明人发现：在用高压合成法制备含有硼的半导体金刚石时，通过向旨在转化为半导体金刚石的石墨材料中按使其均匀的方式加入硼或硼化合物并使其致密、高纯度化、降低氢含量，可以大幅提高作为原料的石墨材料转化为金刚石的转化率，从而完成了本发明。
即，本发明的用于制备半导体金刚石的石墨材料的特征在于：石墨材料含有硼或硼化合物。石墨材料中的硼元素含量为0.1-15质量％，优选0.5-10质量％。石墨的体积密度为1.6g/cm3或以上，优选1.7g/cm3或以上。经过高纯度化处理，石墨材料中的氢含量为1000ppm或以下，优选500ppm或以下，进一步优选50ppm或以下。
附图简述
图1为表示按实施例1的石墨材料的偏光显微镜照片的图。图2为表示按实施例2的石墨材料的偏光显微镜照片的图。图3为用与本发明有关的石墨材料合成金刚石时的带式超高压装置中所用的样品管的剖面图。
发明的最佳实施方式
本发明的用于合成半导体金刚石的石墨材料是使用硼粉或碳化硼粉末、人造石墨粉末、易石墨化碳粉作为原料，将这些原料以任意的方法进行混合、成型、烧结、石墨化、高纯度化而成的。
这里，硼粉或碳化硼粉末并没有特别限定，通常可以使用市售的商品。特别地优选平均粒径为50μm或以下。若平均粒径超过50μm，则在烧结、石墨化处理后，硼成分会不均匀存在于石墨材料中。
作为易石墨化碳粉，可以使用石油焦炭、沥青焦炭、煤焦炭等。其中，通过热处理沥青类生成的中间相小球具有自烧结性，即使不使用粘结剂等也可以进行烧结，因而优选。优选这些易石墨化碳粉的平均粒径为50μm或以下。平均粒径为50μm或以下时，上述硼或碳化硼粉末不会不均匀存在，可以均匀地混合。
与硼粉或碳化硼粉末、易石墨化碳粉同样，也优选人造石墨粉末的平均粒径为50μm或以下。通过使原料粉末的平均粒径一致至相同程度，它们不会各自不均匀地存在，可均匀混合。
接着，将0.1-15质量％、优选0.2-10质量％的硼粉或碳化硼粉末和76-98.9质量％、优选81-98.8质量％的易石墨化碳粉以及1-9质量％的人造石墨粉末以任意的方法混合1-2小时，通过冷各向同性加压法等任意的成型法使其成型为任意的形状、大小。在非氧化气氛下、在600-1300℃温度下进行烧结(一次烧结)。一次烧结后，在惰性气体气氛下、在1800-2200℃、优选在2000℃下进行烧结(二次烧结)。接着在非氧化气氛下、在2400-2600℃温度下进行热处理，进一步提高石墨化度，同时使杂质升华，制成纯度得到提高的石墨材料。通过这些，可以使氢含量为1000ppm或以下。另外，通过提高石墨化度，可以进一步提高金刚石的转化率。
通过这样在2000℃进行烧结，可以使硼成分的挥发损耗大体上得到抑制，制得分散极均匀且机械加工性、热传导率、热膨胀系数等重要物性得到提高的含硼石墨材料。其原因至今尚未清楚，估计是通过在超过硼稳定存在的温度界限下进行加热，反复进行硼成分的游离、向碳部分中转移、扩散、再结合等，硼成分几乎没有损失，极均匀地分散，且由于是高温烧结，使得碳部分的石墨化反应得以进行。另外，由于是这样的高温烧结，可能转变为硼整体均匀分散的固溶体、被硼部分置换的石墨晶体的聚集体、恰如纯石墨材料一样的含硼石墨材料。
通过上述处理，制成了体积密度为1.6g/cm3或以上，优选1.7g/cm3或以上、硼均匀分散的石墨材料。并且可使石墨材料中的硼元素含量为0.1-15质量％、优选0.2-10质量％。体积密度小于1.6g/cm3，则转化为金刚石的转化率变差，因而不优选。通过调节作为原料加入的硼或碳化硼粉末的加入量，该石墨材料中的硼元素含量可以控制在0.1-15质量％、优选0.2-10质量％范围内。硼元素含量比0.1质量％少时，无法在由石墨转换的金刚石中显示显著的半导体特性。含有超过15质量％时，则析出碳化硼，在应用方面不优选。
为了降低石墨材料中的氢等杂质含量，还可以进行高纯度化处理。由此可以进一步提高金刚石的收率。如果石墨材料中含有水分、氢、氧、硫等杂质，特别是即使含有少量氢，石墨材料转化为金刚石的收率则极端降低。因此，最好将在上述高温下进行了石墨化处理的石墨材料在0.1Pa或以下、优选在0.01Pa或以下的压力下，以1800℃或以上的温度进行2小时或以上的热处理。通过该处理，上述石墨材料中的水分、氢、氧、硫等杂质，特别是氢会进一步降低，可使氢含量为1000ppm，优选500ppm，进一步优选50ppm或以下。氢含量由碳/氢/水分分析装置(LECO公司制造，RH-IE型)测定。
通过上述处理，由高压合成法制备金刚石时，与传统的方法相比，可得到转化为含硼半导体金刚石时转化率高的石墨材料。使用这样得到的石墨材料，可以工业化制备半导体金刚石，也可以应用于各种电极、耐化学品性感应器、导电性磨削砂轮等中。
以下通过实施例具体说明本发明。
(实施例1)
将各原料按照碳化硼粉末(平均粒径13μm)15质量％、中间相小球(平均粒径11μm)80质量％、人造石墨粉(平均粒径4μm)5质量％的比例混合，在常温下进行干混1小时，然后用冷各向同性加压法在80MPa的压力下成型，得到120×520×720mm的成形物。将成型物装入焦炭粉末中，在非氧化性气氛下升温至1000℃，得到一次烧结物。在电阻式加热炉内，将该一次烧结物埋于焦炭粉中，在惰性气体气氛中、在2000℃下进行热处理，再在アチエソン(阿切孙)炉中、在2400℃下进行热处理，进一步提高石墨化度，同时使石墨材料中的硼的分散性均匀。该石墨材料的体积密度为1.8g/cm3、肖氏硬度为12、固有电阻为9μΩ·m、弯曲强度为60MPa、压缩强度为65MPa、弹性系数为3GPa、硼元素含量为10质量％、热膨胀系数为2×10-6/℃、热传导率为40W/(m·℃)、氢含量为300ppm。
(实施例2)
除不在アチエソン炉中在2400℃下进行热处理之外，与实施例1同样地制备石墨材料。该石墨材料的体积密度为1.8g/cm3、肖氏硬度为70、固有电阻为15μΩ·m、弯曲强度为60MPa、压缩强度为140MPa、弹性系数为22GPa、硼元素含量为10质量％、热膨胀系数为5×10-6/℃、热传导率为30W/(m·℃)、氢含量为1000ppm以上。
(实施例3)
将实施例2中的石墨材料在2150℃、1.5×10-3Pa的压力下进行热处理。该石墨材料的体积密度为1.8g/cm3、肖氏硬度为70、固有电阻为11μΩ·m、弯曲强度为70MPa、压缩强度为150MPa、弹性系数为20GPa、硼元素含量为10质量％、热膨胀系数为5×10-6/℃、热传导率为35W/(m·℃)、氢含量约为150ppm。
实施例1和实施例2的石墨材料的偏光显微镜照片分别如图1和图2所示。图1和图2表明：实施例1的石墨材料比实施例2的石墨材料的石墨化度高。
接着，分别将实施例1-3的石墨材料加工为_15mm×3mm，使用带式超高压装置转化成金刚石。图3表示该带式超高压装置中所用的样品管的剖面图。图3中，1为砧，2为缸，3为叶腊石衬垫，4为用向食盐中添加混合10％氧化锆粉而形成的成型物制作的绝缘板，5为催化剂金属板，6为本发明的石墨材料，7为用于通电而成为加热器的石墨环。金刚石的合成如图所示，在用与绝缘板4相同材质制的未图示的筒体中，将石墨材料6和催化剂金属板5交替叠层，向配置于该筒体上下的环7通电，在1400℃温度、约5.5GPa的压力下保持30分钟。之后减少对环7的通电，冷却至室温，然后慢慢降低压力，取出样品。将该样品用盐酸、硝酸进行酸处理后回收金刚石。得到的金刚石含有硼，显示半导体的特性。
使用实施例1中的石墨材料时，得到的金刚石的平均粒径为25μm，由石墨材料6转化为金刚石的转化收率为97％。使用实施例2中的石墨材料时，得到的金刚石的平均粒径为25μm，转化为金刚石的转化收率为17％或以下。使用实施例3中的石墨材料时，得到的金刚石的平均粒径为20μm，转化为金刚石的转化收率为99％或以上。这里，金刚石的转化收率可通过测定填充的石墨原料和合成的金刚石的重量来计算。
如上所述，由于提高了石墨材料的石墨化度，降低了石墨中的氢含量，可以特别提高金刚石的收率，可以获得能够按工业化充分制备的金刚石收率。
产业实用性
通过向旨在转化为半导体金刚石的石墨材料中按使其均匀的方式加入硼或硼化合物，使其致密、高纯度化，降低氢含量，可以大幅提高石墨原料转化为金刚石的转化率。由此，可以工业化制备半导体金刚石，也可以应用于各种电极、耐化学的性感应器、导电性磨削砂轮等。

Claims (7)

1.用于合成半导体金刚石的石墨材料，所述石墨材料是在由高压合成法制备半导体金刚石中所采用的石墨材料，它是使用硼粉末或硼化合物粉末、人造石墨粉末、易石墨化碳粉末作为原料，将这些原料粉末以任意的方法进行混合、成型、烧结、石墨化、高纯度化而成的。
2.权利要求1的用于合成半导体金刚石的石墨材料，其中所述硼化合物为碳化硼。
3.权利要求1或2的用于合成半导体金刚石的石墨材料，其中使用所述硼粉末或硼化合物粉末，以使得所述石墨材料中的硼元素含量为0.1-15质量％。
4.权利要求1或2的用于合成半导体金刚石的石墨材料，其中所述石墨材料的体积密度为1.6g/cm3或以上。
5.权利要求1或2的用于合成半导体金刚石的石墨材料，其中所述原料粉末的平均粒径为50μm或以下。
6.权利要求1或2的用于合成半导体金刚石的石墨材料，其中进行高纯度化，以使得所述石墨材料的氢含量达到1000ppm或以下。
7.半导体金刚石，该半导体金刚石使用权利要求1-6中任一项的用于合成半导体金刚石的石墨材料来制备。
CNB018239153A 2001-12-28 2001-12-28 用于合成半导体金刚石的石墨材料以及由该材料制备的半导体金刚石 Expired - Fee Related CN100354199C (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2001/011676 WO2003057625A1 (fr) 2001-12-28 2001-12-28 Materiau graphite permettant de synthetiser un diamant semiconducteur et diamant semiconducteur produit avec ce materiau

Publications (2)

Publication Number Publication Date
CN1582257A CN1582257A (zh) 2005-02-16
CN100354199C true CN100354199C (zh) 2007-12-12

Family

ID=32800785

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB018239153A Expired - Fee Related CN100354199C (zh) 2001-12-28 2001-12-28 用于合成半导体金刚石的石墨材料以及由该材料制备的半导体金刚石

Country Status (7)

Country Link
US (1) US8916125B2 (zh)
EP (1) EP1460040B1 (zh)
JP (1) JP4421745B2 (zh)
KR (1) KR100742059B1 (zh)
CN (1) CN100354199C (zh)
DE (1) DE60130588T2 (zh)
WO (1) WO2003057625A1 (zh)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4421745B2 (ja) * 2001-12-28 2010-02-24 東洋炭素株式会社 半導体ダイヤモンド合成用黒鉛材及び半導体ダイヤモンドの製造方法
WO2006061672A1 (en) * 2004-12-09 2006-06-15 Element Six (Production) (Pty) Ltd Synthesis of diamond
TWI399354B (zh) * 2007-06-07 2013-06-21 Ibiden Co Ltd 石墨材料及石墨材料之製造方法
JP6015325B2 (ja) * 2012-10-09 2016-10-26 住友電気工業株式会社 ダイヤモンド多結晶体およびその製造方法、ならびに工具
CN102989373B (zh) * 2012-11-30 2015-08-12 台钻科技（郑州）有限公司 Hthp合成半导体人造金刚石的方法
CN103752216A (zh) * 2013-11-06 2014-04-30 溧阳市江大技术转移中心有限公司 一种碳化硼焊接料的制造方法
JP7188726B2 (ja) 2017-06-28 2022-12-13 トーメイダイヤ株式会社 ホウ素系結合材を用いたダイヤモンド基複合材及びその製造方法、並びにこれを用いた工具要素

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001170474A (ja) * 1999-12-17 2001-06-26 Natl Inst For Research In Inorganic Materials Mext 導電性ダイヤモンド微粒子の製造方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676069A (en) 1970-08-13 1972-07-11 Teledyne Inc Method for manufacturing diamonds in a hydrogen free environment
JPS596808A (ja) 1982-06-30 1984-01-13 加藤　幾次郎 収穫機におけるホツパ−
US4518702A (en) * 1983-01-19 1985-05-21 Director-General Of The Agency Of Industrial Science And Technology Silicon carbide-boron carbide carbonaceous body
JPS59137396A (ja) 1983-01-25 1984-08-07 Natl Inst For Res In Inorg Mater Ｐ型半導体ダイヤモンドの合成法
JPS63158126A (ja) 1986-12-22 1988-07-01 Natl Inst For Res In Inorg Mater ダイヤモンドの合成方法
JPH02155226A (ja) 1988-12-07 1990-06-14 Toshiba Corp 粒状半導体ダイヤモンドの製造方法
JPH04266020A (ja) 1991-02-20 1992-09-22 Semiconductor Energy Lab Co Ltd 半導体ダイヤモンド
US5266236A (en) * 1991-10-09 1993-11-30 General Electric Company Thermally stable dense electrically conductive diamond compacts
EP0543392A3 (en) * 1991-11-21 1993-10-20 Canon Kk Diamond semiconductor device and method of producing the same
JPH05152604A (ja) 1991-11-29 1993-06-18 Canon Inc ダイヤモンド半導体装置及びその製造方法
JPH05229896A (ja) 1992-02-20 1993-09-07 Matsushita Electric Ind Co Ltd 導電性ダイヤモンドの製造方法
US6342195B1 (en) * 1993-10-01 2002-01-29 The Penn State Research Foundation Method for synthesizing solids such as diamond and products produced thereby
JP3456263B2 (ja) * 1993-10-08 2003-10-14 住友電気工業株式会社 歪みの少ない合成ダイヤモンドおよびその製造方法並びに合成ダイヤモンドの歪み測定方法
KR100269924B1 (ko) 1993-10-08 2000-11-01 하지메 히토추야나기 합성 다이아몬와 그 제조방법
JP3501552B2 (ja) * 1995-06-29 2004-03-02 株式会社神戸製鋼所 ダイヤモンド電極
US5653800A (en) * 1995-08-03 1997-08-05 Eneco, Inc. Method for producing N-type semiconducting diamond
JPH1081588A (ja) 1996-09-05 1998-03-31 Matsushita Electric Ind Co Ltd 半導体ダイヤモンド及びその形成方法
JP3390803B2 (ja) 1997-02-25 2003-03-31 学校法人立命館 ダイヤモンド合成方法及びその装置
JPH11100297A (ja) * 1997-08-01 1999-04-13 Tokyo Gas Co Ltd ホウ素をドープした同位体ダイヤモンド及びその製造方法
US20010001385A1 (en) * 1997-08-01 2001-05-24 Tokyo Gas Co., Ltd Boron-doped isotopic diamond and process for producing the same
JP3660491B2 (ja) 1998-01-23 2005-06-15 昭和電工株式会社 超高圧製品の製造方法
JP4421745B2 (ja) 2001-12-28 2010-02-24 東洋炭素株式会社 半導体ダイヤモンド合成用黒鉛材及び半導体ダイヤモンドの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001170474A (ja) * 1999-12-17 2001-06-26 Natl Inst For Research In Inorganic Materials Mext 導電性ダイヤモンド微粒子の製造方法

Also Published As

Publication number Publication date
JP2002018267A (ja) 2002-01-22
EP1460040A4 (en) 2005-06-08
JP4421745B2 (ja) 2010-02-24
US20050032370A1 (en) 2005-02-10
EP1460040A1 (en) 2004-09-22
CN1582257A (zh) 2005-02-16
DE60130588D1 (de) 2007-10-31
KR20040075325A (ko) 2004-08-27
US8916125B2 (en) 2014-12-23
DE60130588T2 (de) 2008-06-12
KR100742059B1 (ko) 2007-07-23
WO2003057625A1 (fr) 2003-07-17
EP1460040B1 (en) 2007-09-19

Similar Documents

Publication Publication Date Title
Wang et al. Solid–liquid reaction synthesis of layered machinable Ti 3 AlC 2 ceramic
US4469802A (en) Process for producing sintered body of boron nitride
CN102219536A (zh) 一种B4C/SiC晶须/SiC复相陶瓷基复合材料及其制备方法
FI92925B (fi) Menetelmä itsekantavan kappaleen valmistamiseksi ja itsekantava materiaali
CN100354199C (zh) 用于合成半导体金刚石的石墨材料以及由该材料制备的半导体金刚石
JP3669818B2 (ja) 六方晶窒化ほう素粉末
US8426043B2 (en) Boron suboxide composite materials
US5169832A (en) Synthesis of refractory metal boride powders of predetermined particle size
EP1928806A2 (en) Boron suboxide composite material
JP2002284511A (ja) 立方晶窒化ホウ素の製造方法
Bindal et al. High-pressure sintering of cubic boron nitride
JPS61117107A (ja) 非晶質窒化ホウ素粉末およびその製造方法
Keller et al. Direct formulation of nanocrystalline silicon carbide/nitride solid ceramics
JPH05148023A (ja) スピネル、炭化ケイ素、及び炭化ホウ素を含むセラミツク組成物
JP2011068538A (ja) チタンシリコンカーバイドセラミックスの製造方法
JP3553496B2 (ja) 硬質材料の、炭化チタンを基礎にした合金、その製法及び使用法
CN102718488A (zh) 一种铪铝硅碳-碳化硅复合材料及其制备方法
CN103073317A (zh) 一种铝氮化钛／二硼化钛复合材料及其制备方法
JP4165850B2 (ja) 板状晶炭化タングステン含有粉末およびその製造方法
JPS59217608A (ja) 立方晶窒化ほう素の合成法
TW550238B (en) Graphite material for synthesizing semiconductor diamond and semiconductor diamond manufactured using the same
JP3152783B2 (ja) チタン化合物ウイスカーおよびその製造方法並びに複合材料
Hu et al. Synthesis of TiC0. 5–Al and Effect of Sintering Temperature on Mechanical Properties of PcBN Composites
JPH0455144B2 (zh)
JP2794122B2 (ja) 繊維強化セラミックス

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20071212

Termination date: 20151228

EXPY Termination of patent right or utility model