JP4623356B2 - Single crystal diamond - Google Patents
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- JP4623356B2 JP4623356B2 JP2003402410A JP2003402410A JP4623356B2 JP 4623356 B2 JP4623356 B2 JP 4623356B2 JP 2003402410 A JP2003402410 A JP 2003402410A JP 2003402410 A JP2003402410 A JP 2003402410A JP 4623356 B2 JP4623356 B2 JP 4623356B2
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- 239000010432 diamond Substances 0.000 title claims description 96
- 229910003460 diamond Inorganic materials 0.000 title claims description 91
- 239000000758 substrate Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 17
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- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000001069 Raman spectroscopy Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000149 argon plasma sintering Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000012808 vapor phase Substances 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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Description
本発明はダイヤモンドの製造方法に関し、特に半導体材料、電子部品、光学部品などに用いられる、大型のダイヤモンド単結晶に関するものである。 The present invention relates to a method for producing diamond, and more particularly to a large diamond single crystal used for semiconductor materials, electronic parts, optical parts and the like.
ダイヤモンドは高硬度、高熱伝導率、透明度などの数多くの優れた性質を有することから、各種工具、光学部品、半導体、電子部品の材料として幅広く用いられており、この中でも光学部品、半導体にはダイヤモンド単結晶がその良好な光透過性や結晶欠陥の少なさのために必要とされている。今後はさらにダイヤモンド単結晶の重要性が増すものと考えられる。 Since diamond has many excellent properties such as high hardness, high thermal conductivity, and transparency, it is widely used as a material for various tools, optical components, semiconductors, and electronic components. Among them, diamond is used for optical components and semiconductors. Single crystals are needed for their good light transmission and low crystal defects. In the future, the importance of diamond single crystals will increase further.
天然ダイヤモンド単結晶には２３０ｎｍまでの紫外線を透過するIIａ型と呼ばれる品質のものと、紫外線をほとんど透過しないＩａ型と呼ばれる品質のものとがある。いずれの型のものでも直径１０ｍｍ以上の単結晶は入手が極めて困難である。天然では希に２０ｍｍ近い直径の単結晶ダイヤモンドが産出することがあるが、非常に高価で工業用として用いることはできなかった。 There are two types of natural diamond single crystal, the quality called IIa type that transmits ultraviolet rays up to 230 nm, and the quality called Ia type that hardly transmits ultraviolet rays. It is extremely difficult to obtain a single crystal having a diameter of 10 mm or more in any type. Naturally, single crystal diamond with a diameter of nearly 20 mm is rarely produced, but it was very expensive and could not be used for industrial use.
それ以外にも天然に産出するIIａ型は結晶欠陥や歪が多く、例えばＸ線ロッキングカーブの半値幅が角度にして５００秒以上もあることや、１３３２ｃｍ-1付近に観察されるラマン散乱光のスペクトルの半値幅が２ｃｍ-1以上であることなどから、半導体の基板としては不適当であると考えられる。Ｉａ型は３００ｎｍ以下の紫外線を透過しないので紫外線用の光学材料として用いることができないという問題がある。 In addition, naturally occurring type IIa has many crystal defects and distortions, for example, the half width of the X-ray rocking curve is 500 seconds or more in angle, and the Raman scattered light observed near 1332 cm −1 Since the half width of the spectrum is 2 cm −1 or more, it is considered to be inappropriate as a semiconductor substrate. Type Ia has a problem that it cannot be used as an optical material for ultraviolet rays because it does not transmit ultraviolet rays of 300 nm or less.
ダイヤモンドは過去には天然に産出するものが工業用途に使用されたが、現在では工業用は人工合成されたものが中心である。ダイヤモンド単結晶は現在工業的には、全てそれらが安定である数万気圧以上の圧力下で合成されている。このような圧力を発生する超高圧容器は非常に高価であり、内容積を大きくできず、ダイヤモンドを安価に供給できない原因となっている。 In the past, naturally occurring diamonds have been used for industrial purposes, but now industrial ones are mainly artificially synthesized. Diamond single crystals are all industrially synthesized under pressures of tens of thousands of atmospheric pressures at which they are stable. An ultra-high pressure vessel that generates such a pressure is very expensive, the internal volume cannot be increased, and diamond cannot be supplied at a low cost.
このために大型の単結晶を合成することが出来ない。また高圧法で作られたダイヤモンドは窒素が不純物として混入したＩｂ型と呼ばれる結晶になりやすいが、このＩｂ型ダイヤモンドは４００ｎｍ以下の波長の光を全く通さない。これらのことから直径が１０ｍｍ以上で２５０ｎｍ付近の紫外線を透過する人工ダイヤモンド単結晶はこれまで合成できなかった。従来から、気相合成法によって比較的大面積で高純度のダイヤモンドが各種基板上に人工的に製造されていたが、これらは多結晶膜であり単結晶膜は得られていない。 For this reason, a large single crystal cannot be synthesized. Further, diamond produced by the high pressure method tends to be a crystal called Ib type in which nitrogen is mixed as an impurity, but this Ib type diamond does not transmit light having a wavelength of 400 nm or less. From these facts, an artificial diamond single crystal having a diameter of 10 mm or more and transmitting ultraviolet rays of around 250 nm could not be synthesized so far. Conventionally, diamond having a relatively large area and high purity has been artificially produced on various substrates by a vapor phase synthesis method, but these are polycrystalline films, and single crystal films have not been obtained.
しかしながら、ダイヤモンドの用途の中でも特に平滑な面を必要とする超精密工具や光学部品、半導体などに用いられる場合は、単結晶ダイヤモンドを用いることが必要となる。そこで、気相合成法によって単結晶をエピタキシャル成長させる条件が検討されており、さらには気相合成法により大面積の単結晶を製造する方法が検討されている。これまでのところ、ヘテロエピタキシャル成長によって得られたダイヤモンドの単結晶は結晶欠陥が多く、光学用や半導体基板としては充分な品質ではない。 However, it is necessary to use single crystal diamond when it is used for ultra-precision tools, optical parts, semiconductors, etc. that require a smooth surface among diamond applications. Therefore, conditions for epitaxially growing a single crystal by a vapor phase synthesis method have been studied, and further, a method for producing a single crystal having a large area by a vapor phase synthesis method has been studied. So far, diamond single crystals obtained by heteroepitaxial growth have many crystal defects and are not of sufficient quality for optical and semiconductor substrates.
特許文献１には複数の単結晶ダイヤモンドの方位をそろえて並べ、これの上にダイヤモンドを気相合成法により成長させることによりダイヤモンド単結晶を製造する方法が述べられている。面積を大きくすることのみを求めるのであれば、この方法が現在最も優れていると考えられる。 Patent Document 1 describes a method for producing a diamond single crystal by aligning the orientations of a plurality of single crystal diamonds and growing diamonds thereon by a vapor phase synthesis method. If you only want to increase the area, this method is considered the best at present.
しかしながら、この方法においては、どうしても隣り合う単結晶基板界面から成長した部分の結晶性が周囲と比べて劣ってしまう。複数の単結晶基板の方位がずれると、単結晶基板の間にできた小傾角粒界が成長した単結晶中に残って光散乱や電気特性劣化の原因となったり、各単結晶基板の間から結晶方位が異なった異常成長粒子が発生しやすいという問題がある。 However, in this method, the crystallinity of the portion grown from the adjacent single crystal substrate interface is inevitably inferior to the surroundings. If the orientations of multiple single crystal substrates are misaligned, small-angle grain boundaries formed between the single crystal substrates remain in the grown single crystal, causing light scattering and electrical property deterioration, or between each single crystal substrate. Therefore, there is a problem that abnormally grown particles having different crystal orientations are likely to be generated.
特許文献２には、上記のような問題を回避して、複数の基板上に単結晶を成長させるために、上記の方法において、複数の単結晶ダイヤモンドの結晶方位、間隔、高さを調節し、成長温度を適当な範囲に制御することによって、ホモピタキシャル成長を所定の厚みまで維持し、気相合成法の高純度性を活かして、波長２５０ｎｍ付近の紫外域でも透明で、Ｘ線ロッキングカーブの半値幅が１００秒以内またはラマン散乱スペクトルの半値幅が２ｃｍ−１という結晶性の良い１５ｍｍ以上の径を持つ光学用、半導体用の大型ダイヤモンド単結晶を製造することができることが述べられている。 In Patent Document 2, in order to avoid the above problems and grow single crystals on a plurality of substrates, the crystal orientation, interval, and height of the plurality of single crystal diamonds are adjusted in the above method. By controlling the growth temperature within an appropriate range, homopitaxial growth is maintained up to a predetermined thickness, making use of the high purity of the vapor phase synthesis method, and being transparent even in the ultraviolet region near a wavelength of 250 nm, an X-ray rocking curve It is stated that it is possible to produce large diamond single crystals for optics and semiconductors having a diameter of 15 mm or more with good crystallinity, such that the half-value width is less than 100 seconds or the half-value width of the Raman scattering spectrum is 2 cm −1 . .
従来の技術により得られるダイヤモンドは、天然でも人工合成でも、結晶全体にわたって、２５０ｎｍまでの紫外域において透明で、かつ結晶欠陥や歪み、不純物の小さいダイヤモンド単結晶は存在しなかった。具体的には、水素含有量は１０〜１００ｐｐｍ、窒素含有量は５ｐｐｍ以下と少なく、２結晶Ｘ線ロッキングカーブの半値幅が１０〜８０秒と小さいものが存在しなかった。 Diamonds obtained by conventional techniques, whether natural or artificial, were transparent throughout the entire crystal in the ultraviolet region up to 250 nm, and there were no diamond single crystals with small crystal defects, distortion, and impurities. Specifically, the hydrogen content was as low as 10 to 100 ppm and the nitrogen content was as low as 5 ppm or less, and there was no small half width of the double crystal X-ray rocking curve of 10 to 80 seconds.
すなわち、従来のダイヤモンド単結晶は（４００）面のＸ線ロッキングカーブの半値幅が１００秒以内であっても、ダイヤモンドの優れた物性を存分に引き出した半導体デバイスを作製するには不十分であった。
本発明は、２５０ｎｍまでの紫外域において透明で、かつ結晶欠陥や歪み、不純物の小さいダイヤモンド単結晶を提供することを目的とする。
That is, the conventional diamond single crystal is insufficient to produce a semiconductor device that fully draws out the excellent physical properties of diamond even if the half width of the (400) plane X-ray rocking curve is within 100 seconds. there were.
An object of the present invention is to provide a diamond single crystal that is transparent in the ultraviolet region up to 250 nm and has small crystal defects, distortion, and impurities.
本発明は、上記の課題に鑑みてなされたものであり、下記の構成を有する。
（１）結晶全体にわたり、（４００）面Ｘ線ロッキングカーブの半値幅が３２秒以上、８０秒以下の範囲内にあり、かつ炭素原子に対する水素原子の数が、３０ｐｐｍ以上、６０ｐｐｍ以下の範囲内にあり、かつ炭素原子に対する窒素原子の数が５ｐｐｍ以下であることを特徴とする単結晶ダイヤモンド。
（２）室温における熱伝導率が２０００Ｗ／ｍＫ以上、２１５０Ｗ／ｍＫ以下であることを特徴とする上記（１）の単結晶ダイヤモンド。
（３）室温における正孔移動度が１７００ｃｍ ２ ／Ｖｓｅｃ以上、１８００ｃｍ ２ ／Ｖｓｅｃ以下であることを特徴とする上記（１）又は（２）の単結晶ダイヤモンド。
（４）室温における電子移動度が１６５０ｃｍ ２ ／Ｖｓｅｃ以上、１７００ｃｍ ２ ／Ｖｓｅｃ以下であることを特徴とする上記（１）〜（３）の単結晶ダイヤモンド。
（５）ラマン分光におけるラマンシフト１３３２ｃｍ−１に現れるピークの半値幅が１．６ｃｍ −１ 以上、１．７ｃｍ −１ 以下であることを特徴とする（１）〜（４）の単結晶ダイヤモンド。
（６）波長２５０ｎｍにおける透過率が６０％以上、６３％以下であることを特徴とする上記（１）〜（５）の単結晶ダイヤモンド。
The present invention has been made in view of the above problems, and has the following configuration.
(1) Over the entire crystal, the full width at half maximum of the (400) plane X-ray rocking curve is in the range of not less than 32 seconds and not more than 80 seconds, and the number of hydrogen atoms relative to carbon atoms is in the range of not less than 30 ppm and not more than 60 ppm. A single crystal diamond characterized in that the number of nitrogen atoms relative to carbon atoms is 5 ppm or less.
( 2 ) The single crystal diamond according to the above (1) , wherein the thermal conductivity at room temperature is 2000 W / mK or more and 2150 W / mK or less .
( 3 ) The single crystal diamond according to (1) or (2) above , wherein the hole mobility at room temperature is 1700 cm 2 / Vsec or more and 1800 cm 2 / Vsec or less .
(4) an electron mobility of 1650 cm 2 / Vsec or more at room temperature, the is equal to or less than 1700 cm 2 / Vsec (1) single-crystal diamond to (3).
(5) half-value width of the peak appearing in the Raman shift 1332 cm -1 in the Raman spectroscopy 1.6 cm -1 or more, and wherein the at 1.7 cm -1 or less (1) single-crystal diamond to (4).
( 6 ) The single crystal diamond according to the above (1) to ( 5 ), wherein the transmittance at a wavelength of 250 nm is 60% or more and 63% or less .
（７）水素プラズマ処理により現れる表面エッチピットが１平方センチメートルあたり１．５×１０ ４ 個以上、１．８×１０ ４ 個以下であることを特徴とする請求項１〜６のいずれかに記載の結晶ダイヤモンド。
（８）光散乱トモグラフ法によって評価した結晶欠陥の数が、１平方センチメートルあたり１．７×１０ ４ 個以上、１．９×１０ ４ 個以下であることを特徴とする上記（１）〜（７）の単結晶ダイヤモンド。
（９）ヤング率が９．９×１０ １１ Ｐａ以上、１．０８×１０ １２ Ｐａ以下であることを特徴とする上記（１）〜（８）の単結晶ダイヤモンド。
（１０）差し渡し径が１３．５ｍｍ以上、３４ｍｍ以下であることを特徴とする上記（１）〜（９）の単結晶ダイヤモンド。
（１１）上記（１）〜（１０）の単結晶ダイヤモンドからなる半導体基板。
（１２）上記（１）〜（１１）の単結晶ダイヤモンドからなる光学窓。
( 7 ) Surface etch pits appearing by hydrogen plasma treatment are 1.5 × 10 4 or more and 1.8 × 10 4 or less per square centimeter, according to any one of claims 1 to 6 Crystal diamond.
( 8 ) The number of crystal defects evaluated by the light scattering tomography method is 1.7 × 10 4 or more and 1.9 × 10 4 or less per square centimeter, (1) to ( 7 ) Single crystal diamond.
( 9 ) The single crystal diamond according to the above (1) to ( 8 ), wherein the Young's modulus is 9.9 × 10 11 Pa or more and 1.08 × 10 12 Pa or less .
( 10 ) The single crystal diamond according to any one of (1) to ( 9 ) above, wherein a passing diameter is 13.5 mm or more and 34 mm or less .
( 11 ) A semiconductor substrate comprising the single crystal diamond of (1) to ( 10 ) above.
( 12 ) An optical window comprising the single crystal diamond of the above (1) to (11).
このように大型でかつ高純度、高品質のダイヤモンド単結晶は、天然でも、人工合成でも得られたことが無く、これまで適用が難しかった半導体基板用途や、窓材などの光学部品用途に途を開くものである。 Such large, high-purity, high-quality diamond single crystals have never been obtained by either natural or artificial synthesis, and have been used for semiconductor substrate applications and optical component applications such as window materials that have been difficult to apply. Open.
本発明の均質で大型かつ大面積のダイヤモンド単結晶は光学用、半導体基板として使用できので、半導体基材、放熱基板、光学材料の素材として幅広く用いることができる。 The homogeneous, large, and large area diamond single crystal of the present invention can be used as a semiconductor substrate for optics and a semiconductor substrate, and therefore can be widely used as a material for semiconductor substrates, heat dissipation substrates, and optical materials.
複数の単結晶基板の方位がずれると、単結晶基板の間にできた小傾角粒界が成長した単結晶中に残って光散乱や電気特性劣化の原因となったり、各単結晶基板の間から結晶方位が異なった異常成長粒子が発生しやすいという問題がある。このような問題を回避して、複数の基板上に単結晶を成長させるために、特許文献２には、単結晶基板の成長面を（１００）面から３度以内の面とすること、各単結晶基板の方位のずれを３度以内に抑えること、隣り合う単結晶基板間の距離を３０μｍ以内にすること、成長温度を１０００℃以上の高温とすること、単結晶基板同士の高さを揃えること等の工夫が開示されている。 If the orientations of multiple single crystal substrates are misaligned, small-angle grain boundaries formed between the single crystal substrates remain in the grown single crystal, causing light scattering and electrical property deterioration, or between each single crystal substrate. Therefore, there is a problem that abnormally grown particles having different crystal orientations are likely to be generated. In order to avoid such a problem and grow a single crystal on a plurality of substrates, Patent Document 2 discloses that the growth surface of the single crystal substrate is a surface within 3 degrees from the (100) plane, To suppress the deviation of the orientation of single crystal substrates within 3 degrees, to set the distance between adjacent single crystal substrates within 30 μm, to set the growth temperature to a high temperature of 1000 ° C. or higher, and to increase the height between the single crystal substrates. Devices such as aligning are disclosed.
本発明では、さらに使用するダイヤモンド単結晶基板の、ダイヤモンドを成長させる主面は、その面粗さがＲmax０．０５μｍ以下であり、全面が（１００）セクタで構成されているものを用いる。このような表面を有するダイヤモンド単結晶基板上に、気相合成法によりダイヤモンドを成長させる。成長させる条件は、炭素源となる炭素含有化合物ガスと水素ガスの比率が、炭素含有化合物中の炭素原子数／水素ガス中の水素原子数で表して、０．０２５〜０．０７５であること、基板温度は８５０℃以上９５０℃未満であることが好ましいことを見出した。 In the present invention, the main surface of the diamond single crystal substrate to be used for growing diamond has a surface roughness of Rmax 0.05 μm or less and the entire surface is composed of (100) sectors. Diamond is grown on the diamond single crystal substrate having such a surface by vapor phase synthesis. The growth condition is that the ratio of the carbon-containing compound gas to the carbon source and the hydrogen gas is 0.025 to 0.075 in terms of the number of carbon atoms in the carbon-containing compound / number of hydrogen atoms in the hydrogen gas. The substrate temperature was found to be preferably 850 ° C. or higher and lower than 950 ° C.
すなわち、本発明の単結晶は、次の条件を満たすことによって製造することができる。
ａ．単結晶基板の成長面の全面が（１００）セクタで構成されているものを用いる。
ｂ．単結晶基板の成長面を（１００）面から３度以内の面とする。
ｃ．各単結晶基板の方位のずれを３度以内に抑える。
ｄ．隣り合う単結晶基板間の距離を３０μｍ以内にする。
ｅ．単結晶基板同士の高さを揃える。
ｆ．ダイヤモンドを成長させる主面の面粗さをＲmax０．０５μｍ以下とする。
であり、
ｇ．上記ダイヤモンド単結晶基板上に、炭素源となる炭素含有化合物ガスと水素ガスの比率が、炭素含有化合物中の炭素原子数／水素ガス中の水素原子数で表して、０．０２５〜０．０７５であり、基板温度を８５０℃以上９５０℃未満である気相合成法によりダイヤモンドを成長させる。
That is, the single crystal of the present invention can be manufactured by satisfying the following conditions.
a. A single crystal substrate whose growth surface is entirely composed of (100) sectors is used.
b. The growth surface of the single crystal substrate is a surface within 3 degrees from the (100) surface.
c. The deviation of the orientation of each single crystal substrate is suppressed to within 3 degrees.
d. The distance between adjacent single crystal substrates is set within 30 μm.
e. Align the height of single crystal substrates.
f. The surface roughness of the main surface on which diamond is grown is set to Rmax 0.05 μm or less.
And
g. On the diamond single crystal substrate, the ratio of the carbon-containing compound gas serving as the carbon source and the hydrogen gas is expressed by the number of carbon atoms in the carbon-containing compound / number of hydrogen atoms in the hydrogen gas. The diamond is grown by a vapor phase synthesis method in which the substrate temperature is 850 ° C. or higher and lower than 950 ° C.
このような条件および基板を用いることによって、得られるダイヤモンド単結晶は、差し渡し径１０ｍｍ以上で、（４００）面におけるＸ線ロッキングカーブの半値幅が３２秒以上、８０秒以下、水素含有量３０ｐｐｍ以上、６０ｐｐｍ以下、窒素含有量５ｐｐｍ以下、室温における熱伝導率が２０００Ｗ／ｍＫ以上、２１５０Ｗ／ｍＫ以下、正孔移動度１５００ｃｍ２／Ｖｓｅｃ以上、電子移動度１５００ｃｍ２／Ｖｓｅｃ以上、ラマン分光半値幅２ｃｍ−１以下、波長２５０ｎｍにおける透過率３０％以上、水素プラズマ処理により表面に現れるエッチピットの数が１平方センチメートルあたり１×１０５個以下、光散乱トモグラフ法によって評価した結晶欠陥の数が、１×１０５ｃｍ−２以下、ヤング率が５×１０１１Ｐａ以上である、これまで天然にもなく、人工でも得ることの出来なかった半導体基板、窓材として非常に優れたものが得られる。 By using such a condition and the substrate, the obtained diamond single crystal has a passing diameter of 10 mm or more, a half width of the X-ray rocking curve in the (400) plane of 32 seconds or more, 80 seconds or less , and a hydrogen content of 30 ppm or more. , 60 ppm or less, the nitrogen content 5ppm or less, the thermal conductivity of 2000 W / mK or more at room temperature, 2150W / mK or less, the hole mobility 1500 cm 2 / Vsec or more, the electron mobility of 1500 cm 2 / Vsec or more, Raman spectroscopy FWHM 2cm −1 or less, transmittance of 30% or more at a wavelength of 250 nm, the number of etch pits appearing on the surface by hydrogen plasma treatment is 1 × 10 5 or less per square centimeter, and the number of crystal defects evaluated by light scattering tomography is 1 × 10 5 cm −2 or less, Young's modulus of 5 × 10 11 Pa or more It is possible to obtain a semiconductor substrate and a window material that have never been obtained by nature and that have not been obtained artificially.
通常、気相合成法によれば、プロセスガス中に水素を大過剰含むために、得られるダイヤモンド中にも水素の混入が避けられず、これが得られるダイヤモンドの光学的、電気的物性を劣化させる原因の一つと考えられてきた。本願発明において開示された成長方法を適用することによって、水素不純物の量を減らすと共に、水素が存在していても、光学用途や半導体デバイス用途に充分な性質を持ったダイヤモンド単結晶が得られることがわかった。 Normally, according to the gas phase synthesis method, hydrogen is inevitably mixed in the resulting diamond because the process gas contains a large excess of hydrogen, which deteriorates the optical and electrical properties of the resulting diamond. It has been considered one of the causes. By applying the growth method disclosed in the present invention, the amount of hydrogen impurities can be reduced, and even if hydrogen is present, a diamond single crystal having properties sufficient for optical applications and semiconductor device applications can be obtained. I understood.
本発明において差し渡し径とは、ある大きさ、形を持つ単結晶内に引くことのできる最大の直線の長さのことである。 In the present invention, the span diameter is the maximum length of a straight line that can be drawn in a single crystal having a certain size and shape.
本発明におけるダイヤモンド単結晶を成長させる気相合成法は、熱フィラメントＣＶＤ法、プラズマＣＶＤ法、プラズマジェット法、燃焼炎法、レーザーＣＶＤ法などの既知の方法のいずれであっても良い。また、原料ガスとしては、炭化水素などの炭素を含む物質で良く、例えば、メタン、エタン、プロパン、メタノール、エタノール、エチレン、アセチレン、ベンゼン、等が挙げられる。本発明のダイヤモンド単結晶を成長させる際に用いる基板は、高圧合成による人工ダイヤモンド単結晶が最も品質も揃ったものが入手できるので好ましいが、天然単結晶や気相成長させた単結晶を基板として用いることも勿論可能である。 The vapor phase synthesis method for growing a diamond single crystal in the present invention may be any of known methods such as a hot filament CVD method, a plasma CVD method, a plasma jet method, a combustion flame method, and a laser CVD method. The source gas may be a substance containing carbon such as hydrocarbon, and examples thereof include methane, ethane, propane, methanol, ethanol, ethylene, acetylene, and benzene. The substrate used for growing the diamond single crystal of the present invention is preferably an artificial diamond single crystal obtained by high-pressure synthesis having the highest quality, but it is preferable to use a natural single crystal or a vapor-grown single crystal as the substrate. Of course, it can be used.
以下、実施例及び比較例によって本願発明を説明する。
各実施例及び比較例によって得られた試料の評価結果を下記表１に示したが、表中の各評価項目の意味するところは次の通りである。
The present invention will be described below with reference to examples and comparative examples.
The evaluation results of the samples obtained in each Example and Comparative Example are shown in Table 1 below. The meaning of each evaluation item in the table is as follows.
［評価項目］
「差し渡し径」とは、最大の差し渡し長さ［ｍｍ］である。
「ＸＲＣ」とは（４００）面のＸ線ロッキングカーブの半値幅［秒］である。
本発明におけるＸＲＣとは、ＣｕＫα１のＸ線を用いて、第一結晶として高圧合成単結晶ダイヤモンド（４００）面平行配置を利用して２結晶法により評価したものをいう。
[Evaluation item]
The “passing diameter” is the maximum passing length [mm].
“XRC” is the half-value width [second] of the X-ray rocking curve of the (400) plane.
In the present invention, XRC refers to an evaluation by a two-crystal method using CuKα1 X-rays and using a high-pressure synthetic single crystal diamond (400) plane parallel arrangement as a first crystal.
「Ｈ」とは、炭素原子に対する水素原子の数［ｐｐｍ］である。
「Ｎ」とは、炭素原子に対する窒素原子の数［ｐｐｍ］である。
「２５０ｎｍ」とは、波長２５０ｎｍにおける透過率［％］である。
「熱伝導率」とは、室温における熱伝導率［Ｗ／ｍ・Ｋ］である。
「電子移動度」とは室温における電子移動度［ｃｍ２／Ｖ・ｓ］である。
「正孔移動度」とは、室温におけるホール移動度［ｃｍ２／Ｖ・ｓ］である。
“H” is the number [ppm] of hydrogen atoms relative to carbon atoms.
“N” is the number of nitrogen atoms [ppm] relative to carbon atoms.
“250 nm” is the transmittance [%] at a wavelength of 250 nm.
“Thermal conductivity” is the thermal conductivity [W / m · K] at room temperature.
The “electron mobility” is the electron mobility [cm 2 / V · s] at room temperature.
“Hole mobility” is the hole mobility [cm 2 / V · s] at room temperature.
「ラマン」とは、波長５１４．５ｎｍのアルゴンイオンレーザーを励起光として、顕微ラマン分光法により評価したときに、励起光から１３３２ｃｍ−１の位置にシフトして現れるラマン散乱スペクトルの半値幅［ｃｍ−１］のことである。分解能０．５ｃｍ−１の分光器で測定した。 “Raman” means a half-value width [cm] of a Raman scattering spectrum that appears by shifting to a position of 1332 cm −1 from the excitation light when evaluated by microscopic Raman spectroscopy using an argon ion laser having a wavelength of 514.5 nm as excitation light. −1 ]. Measurement was performed with a spectrometer having a resolution of 0.5 cm −1 .
「水素プラズマ」とは、マイクロ波プラズマＣＶＤ法により生成した水素プラズマに、得られたダイヤモンド単結晶を曝して、欠陥に由来するエッチピットを表面に生成させた時に生じるエッチピットの数［個／ｃｍ２］である。用いた水素プラズマは、圧力９．３ｋＰａ、基板温度８２０℃であった。
「トモグラフ」とは、光散乱トモグラフ法により、ダイヤモンド単結晶内部の結晶欠陥の数を評価したもの［個／ｃｍ２］である。
「ヤング率」は、室温におけるヤング率［Ｐａ］である。
“Hydrogen plasma” refers to the number of etch pits generated when the obtained diamond single crystal is exposed to hydrogen plasma generated by a microwave plasma CVD method to generate etch pits derived from defects on the surface [piece / cm 2 ]. The hydrogen plasma used had a pressure of 9.3 kPa and a substrate temperature of 820 ° C.
The “tomograph” is an evaluation [number / cm 2 ] of the number of crystal defects inside the diamond single crystal by a light scattering tomography method.
“Young's modulus” is the Young's modulus [Pa] at room temperature.
大きさ４．０ｍｍ×４．０ｍｍ×３００±２０μｍのダイヤモンド｛１００｝基板３６枚を、間隔１０μｍ以内になるように、縦横６列ずつに並べた。これらの基板は、全て表面が（１００）セクタで構成されているものを選択し、かつ、機械加工により表面の面粗さをＲｍａｘ０．０５μｍ以下とした。さらに（１００）面からのオフ角が、±１．５°以下であるものを選択した。各基板間の方位のずれは、最大２．１°であった。 Thirty-six diamond {100} substrates having a size of 4.0 mm × 4.0 mm × 300 ± 20 μm were arranged in 6 rows vertically and horizontally so that the distance was within 10 μm. All of these substrates were selected so that the surface was composed of (100) sectors, and the surface roughness was set to Rmax 0.05 μm or less by machining. Further, the one having an off angle from the (100) plane of ± 1.5 ° or less was selected. The maximum misalignment between the substrates was 2.1 °.
このように選択、配置した基材上に、マイクロ波プラズマＣＶＤ法によりダイヤモンドを成長させた。メタン濃度７％、圧力１２．７ｋＰａ、基材温度９００℃で通算５０時間の成長を行うことにより、３６枚の基材上に４１０μｍの厚さのダイヤモンドを形成した後、両面を機械研磨した。さらに、反応性イオンエッチング法により基材を除去した。用いた条件はＣＦ４１％−Ｏ２混合ガスを用い、圧力５Ｐａ、高周波周波数１３．５６ＭＨｚ、高周波電力２４０Ｗである。合計７０時間の処理により、基材は全てエッチング除去され、２５．１ｍｍ×２５．０ｍｍ×３８０μｍの一体となったダイヤモンド単結晶が得られた（試料Ａ）。最大差し渡し径は３４ｍｍであった。 On the substrate thus selected and arranged, diamond was grown by the microwave plasma CVD method. Growth was performed at a methane concentration of 7%, a pressure of 12.7 kPa, and a substrate temperature of 900 ° C. for a total of 50 hours to form 410 μm thick diamond on 36 substrates, and then both surfaces were mechanically polished. Further, the substrate was removed by a reactive ion etching method. The conditions used were CF 4 1% -O 2 mixed gas, pressure 5 Pa, high frequency frequency 13.56 MHz, high frequency power 240 W. By the treatment for a total of 70 hours, all the base material was removed by etching, and a diamond single crystal integrated with 25.1 mm × 25.0 mm × 380 μm was obtained (Sample A). The maximum delivery diameter was 34 mm.
このダイヤモンド単結晶の特性を下記の通り評価したところ、結晶全体にわたり優れた結晶性、電気特性、光学特性を有することが判り、半導体基板、および光学部品として優れた素材であることがわかった。 When the characteristics of this diamond single crystal were evaluated as follows, it was found that the entire crystal had excellent crystallinity, electrical characteristics, and optical characteristics, and it was found to be an excellent material for semiconductor substrates and optical components.
１）結晶性
（４００）面のＸ線ロッキングカーブの半値幅を評価した。ＣｕＫα１のＸ線を用いて、第一結晶として高圧合成単結晶ダイヤモンド（４００）面平行配置を利用して２結晶法により評価した。その結果、半値幅は全面にわたり３２〜７０秒の範囲内に入り、良好であった。
1) Crystallinity The half width of the (400) plane X-ray rocking curve was evaluated. Evaluation was made by a two-crystal method using a high-pressure synthetic single crystal diamond (400) plane parallel arrangement as a first crystal using X-rays of CuKα1. As a result, the full width at half maximum was in the range of 32 to 70 seconds over the entire surface, which was good.
２）不純物
赤外透過吸収法により結晶中に含まれる水素濃度を定量した。その結果、結晶全面にわたり水素は炭素に対して３０〜６０ｐｐｍの範囲に入り、低濃度であることがわかった。また、紫外光吸収法により、結晶中に含まれる窒素濃度を定量した。その結果、結晶全面にわたり、窒素は炭素に対して３ｐｐｍ以下と低濃度であることがわかった。また、波長２５０ｎｍにおける透過率は、試料全面にわたって最低でも６０％以上であった。
2) Impurities The concentration of hydrogen contained in the crystals was quantified by an infrared transmission absorption method. As a result, it was found that hydrogen entered the range of 30 to 60 ppm with respect to the carbon over the entire surface of the crystal, and had a low concentration. Further, the concentration of nitrogen contained in the crystal was quantified by an ultraviolet light absorption method. As a result, it was found that nitrogen was a low concentration of 3 ppm or less with respect to carbon over the entire crystal surface. Further, the transmittance at a wavelength of 250 nm was at least 60% over the entire surface of the sample.
３）熱伝導率
得られたダイヤモンド単結晶の熱伝導率を、定常比較法により測定した。その結果、熱伝導率は３０℃において２１００±５０Ｗ／ｍＫであることがわかった。
3) Thermal conductivity The thermal conductivity of the obtained diamond single crystal was measured by a steady comparison method. As a result, it was found that the thermal conductivity was 2100 ± 50 W / mK at 30 ° C.
４）電気特性
得られたダイヤモンド単結晶の電子移動度、および正孔移動度を、ＴＯＦ法により評価したところ、それぞれ２５℃において１６５０ｃｍ２／Ｖ・ｓｅｃ，１８００ｃｍ２／Ｖ・ｓｅｃとなり、優れた電気特性を有していることが判った。
4) the electron mobility of the electrical properties resulting diamond single crystal, and the hole mobility was evaluated by TOF method, 1650cm 2 / V · sec at 25 ° C., respectively, 1800cm 2 / V · sec, and the good It was found to have electrical characteristics.
５）ラマン分光
波長５１４．５ｎｍのアルゴンイオンレーザーを励起光として、顕微ラマン分光法により得られたダイヤモンド単結晶を評価した。その結果、励起光から１３３２ｃｍ−１の位置にシフトして現れるラマン散乱スペクトルの半値幅は、分解能０．５ｃｍ−１の分光器で測定して１．６ｃｍ−１であった。
5) Raman spectroscopy Diamond single crystals obtained by microscopic Raman spectroscopy were evaluated using an argon ion laser having a wavelength of 514.5 nm as excitation light. As a result, the half-width of the Raman scattering spectrum appears shifted from the excitation light to the position of 1332 cm -1 was 1.6 cm -1 as measured by a spectroscope resolution 0.5 cm -1.
６）結晶欠陥
結晶中に含まれる欠陥を評価するために、エッチピットを調べた。マイクロ波プラズマＣＶＤ法により生成した水素プラズマに、得られたダイヤモンド単結晶を曝して、欠陥に由来するエッチピットを表面に生成させた。用いた水素プラズマは、圧力９．３ｋＰａ、基板温度８２０℃であった。その結果、試料全面にわたって、生成したエッチピットの密度は２×１０４ｃｍ−２以下であった。
また、得られた単結晶ダイヤモンドの外周部をレーザー切断し、切断した１側面を機械研磨した上で、アルゴンイオンレーザーを側面から照射し、表面から、欠陥に起因する光散乱を評価した（光散乱トモグラフ法）。その結果、結晶欠陥の数は１．７×１０４ｃｍ−２であった。エッチピット評価結果とあわせ、非常に良好な結晶であることがわかった。
6) Crystal defects Etch pits were examined in order to evaluate defects contained in the crystals. The obtained diamond single crystal was exposed to hydrogen plasma generated by a microwave plasma CVD method to generate etch pits derived from defects on the surface. The hydrogen plasma used had a pressure of 9.3 kPa and a substrate temperature of 820 ° C. As a result, the density of the generated etch pits was 2 × 10 4 cm −2 or less over the entire surface of the sample.
Further, the outer periphery of the obtained single crystal diamond was laser-cut, and one side of the cut was mechanically polished, and then irradiated with an argon ion laser from the side, and light scattering caused by defects was evaluated from the surface (light Scattering tomography method). As a result, the number of crystal defects was 1.7 × 10 4 cm −2 . Together with the results of the etch pit evaluation, it was found that the crystals were very good.
７）ヤング率
得られた単結晶ダイヤモンドのヤング率を、３点曲げ試験法により評価した。その結果、９９０ＧＰａであった。
7) Young's modulus The Young's modulus of the obtained single crystal diamond was evaluated by a three-point bending test method. As a result, it was 990 GPa.
大きさ８ｍｍ×８ｍｍ×３５０μｍの天然ダイヤモンドＩｂ｛１００｝基板を用意した。この基板は、表面が（１００）セクタで構成されているものを選択し、かつ、機械加工により表面の面粗さをＲmax ０．０３μｍ以下とした。（１００）面からのオフ角は、０．８°であった。 A natural diamond Ib {100} substrate having a size of 8 mm × 8 mm × 350 μm was prepared. For this substrate, a substrate whose surface is composed of (100) sectors was selected, and the surface roughness of the substrate was set to Rmax 0.03 μm or less by machining. The off angle from the (100) plane was 0.8 °.
この基材上に、マイクロ波プラズマＣＶＤ法によりダイヤモンドを成長させた。メタン濃度８％、圧力１２ｋＰａ、基材温度８８０℃で通算７０時間の成長を行うことにより、基材上に５６０μｍの厚さのダイヤモンドを形成した後、成長表面を機械研磨した。さらに、反応性イオンエッチング法により基材を除去した。用いた条件はＣＦ４ １％−Ｏ２混合ガスを用い、圧力５Ｐａ、高周波周波数１３．５６ＭＨｚ、高周波電力２４０Ｗである。合計７５時間の処理により、基材は全てエッチング除去され、９ｍｍ×９ｍｍ×４５０μｍのダイヤモンド単結晶（試料Ｂ）が得られた。最大差し渡し径は１３．５ｍｍであった。
このダイヤモンド単結晶を、実施例１と同様に評価した。得られた結果は表１に示す。光学的、電気的に優れた物性を示す、大型で均一な単結晶であることがわかり、半導体基板、および光学部品として優れた素材であることがわかった。
On this base material, diamond was grown by the microwave plasma CVD method. By growing at a methane concentration of 8%, a pressure of 12 kPa, and a substrate temperature of 880 ° C. for a total of 70 hours, a diamond having a thickness of 560 μm was formed on the substrate, and then the growth surface was mechanically polished. Further, the substrate was removed by a reactive ion etching method. The conditions used were CF 4 1% -O 2 mixed gas, pressure 5 Pa, high frequency frequency 13.56 MHz, high frequency power 240 W. Through the treatment for a total of 75 hours, all the base material was removed by etching, and a 9 mm × 9 mm × 450 μm diamond single crystal (sample B) was obtained. The maximum delivery diameter was 13.5 mm.
This diamond single crystal was evaluated in the same manner as in Example 1. The results obtained are shown in Table 1. It was found to be a large and uniform single crystal exhibiting excellent optical and electrical properties, and was found to be an excellent material for semiconductor substrates and optical components.
［比較例］
天然ダイヤモンド単結晶IIａ型２個（試料Ｃ、Ｄ）、Ｉａ型２個（試料Ｅ、Ｆ）、高圧合成Ｉｂ型単結晶３個（Ｇ、Ｈ、Ｉ）、高圧合成IIａ型単結晶１個（Ｊ）、気相合成ダイヤモンド単結晶１個（Ｋ）を、本件発明の実施例と同様に特性を評価して調べたところ表１のようになった。いずれも、上記実施例と同様の条件で評価を行っている。この測定結果から本発明のダイヤモンドはこれまでに得られなかった大型高品質のダイヤモンドであることが判明した。試料Ｃ〜Ｆにおいては、正孔移動度、電子移動度共に非常に低く、測定限界以下であった。
[Comparative example]
Two natural diamond single crystals IIa (samples C and D), two Ia (samples E and F), three high-pressure synthetic Ib single crystals (G, H, I), and one high-pressure synthetic IIa single crystal When (J), one vapor-phase synthetic diamond single crystal (K) was evaluated by examining the characteristics in the same manner as in the examples of the present invention, it was as shown in Table 1. In any case, the evaluation is performed under the same conditions as in the above example. From this measurement result, it was found that the diamond of the present invention was a large, high-quality diamond that had not been obtained so far. In Samples C to F, both hole mobility and electron mobility were very low and were below the measurement limit.
気相合成ダイヤモンド単結晶（試料Ｋ）は、下記のように作製した。
大きさ４．０ｍｍ×４．０ｍｍ×３００±２０μｍのダイヤモンド｛１００｝基板３６枚を、間隔１０μｍ以内になるように、縦横６列ずつに並べた。これらの基板は、セクタ表面を特に（１００）面とは規定せず選択した。面粗さはＲmax＝０．１μｍであった。さらに、（１００）面からのオフ角が、３６枚中２０枚において、３°以上４°以下であるものを選択した。
A gas phase synthetic diamond single crystal (sample K) was prepared as follows.
Thirty-six diamond {100} substrates having a size of 4.0 mm × 4.0 mm × 300 ± 20 μm were arranged in 6 rows vertically and horizontally so that the distance was within 10 μm. In these substrates, the sector surface was not particularly defined as the (100) plane and was selected. The surface roughness was Rmax = 0.1 μm. Furthermore, the off angle from the (100) plane was selected to be 3 ° or more and 4 ° or less in 20 of 36 sheets.
本発明のダイヤモンド単結晶は、２５０ｎｍまでの紫外域において透明で、かつ結晶欠陥や歪みが小さく、不純物濃度も少ないので、半導体基板や、窓材などの光学部品用の材料として用いることができる。 The diamond single crystal of the present invention is transparent in the ultraviolet region up to 250 nm, has small crystal defects and distortions, and has a low impurity concentration. Therefore, it can be used as a material for optical components such as semiconductor substrates and window materials.
Claims (12)
（４００）面Ｘ線ロッキングカーブの半値幅が３２秒以上、８０秒以下の範囲内にあり、かつ
炭素原子に対する水素原子の数が、３０ｐｐｍ以上、６０ｐｐｍ以下の範囲内にあり、かつ
炭素原子に対する窒素原子の数が５ｐｐｍ以下である
ことを特徴とする単結晶ダイヤモンド。 Throughout the crystal,
The full width at half maximum of the (400) plane X-ray rocking curve is in the range of not less than 32 seconds and not more than 80 seconds, and the number of hydrogen atoms relative to the carbon atom is in the range of not less than 30 ppm and not more than 60 ppm. A single-crystal diamond characterized in that the number of nitrogen atoms is 5 ppm or less.
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| EP2226413B1 (en) * | 2007-12-26 | 2016-10-12 | Sumitomo Electric Industries, Ltd. | Method for manufacturing diamond monocrystal having a thin film, and diamond monocrystal having a thin film. |
| JP5831795B2 (en) * | 2011-09-06 | 2015-12-09 | 住友電気工業株式会社 | Diamond composite and single crystal diamond separated therefrom |
| JP2013203596A (en) * | 2012-03-28 | 2013-10-07 | National Institute Of Advanced Industrial Science & Technology | Single crystal diamond substrate |
| WO2014168053A1 (en) | 2013-04-09 | 2014-10-16 | 住友電気工業株式会社 | Single crystal diamond and diamond tool |
| EP2848716B1 (en) | 2013-04-30 | 2019-12-25 | Sumitomo Electric Industries, Ltd. | Single crystal diamond and diamond tool |
| JP6312236B2 (en) * | 2013-09-30 | 2018-04-18 | 国立研究開発法人産業技術総合研究所 | Method for producing single crystal diamond |
| GB201320304D0 (en) * | 2013-11-18 | 2014-01-01 | Element Six Ltd | Methods of fabricating synthetic diamond materials using microwave plasma actived chemical vapour deposition techniques and products obtained using said |
| JP6636239B2 (en) * | 2014-08-29 | 2020-01-29 | 国立大学法人電気通信大学 | Method for producing single crystal diamond, single crystal diamond, method for producing single crystal diamond substrate, single crystal diamond substrate and semiconductor device |
| JP6374060B2 (en) * | 2017-06-27 | 2018-08-15 | 国立研究開発法人産業技術総合研究所 | Method for producing single crystal diamond |
| JP6746124B2 (en) * | 2019-06-26 | 2020-08-26 | 国立研究開発法人産業技術総合研究所 | Method for producing single crystal diamond |
| WO2022210936A1 (en) * | 2021-03-31 | 2022-10-06 | 住友電気工業株式会社 | Single crystal diamond and method for producing same |
| CN116964258A (en) * | 2021-03-31 | 2023-10-27 | 住友电气工业株式会社 | Single crystal diamond and method for producing same |
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| JPH0492896A (en) * | 1990-08-09 | 1992-03-25 | Sumitomo Electric Ind Ltd | Vapor-phase synthesized diamond |
| JPH0717794A (en) * | 1993-06-30 | 1995-01-20 | Sumitomo Electric Ind Ltd | Diamond single crystal |
| JPH09165295A (en) * | 1994-12-05 | 1997-06-24 | Sumitomo Electric Ind Ltd | Diamond single crystal little in defect and synthetic method therefor |
| WO2001096633A1 (en) * | 2000-06-15 | 2001-12-20 | Element Six (Pty) Ltd | Single crystal diamond prepared by cvd |
| JP2003277183A (en) * | 2002-03-22 | 2003-10-02 | Sumitomo Electric Ind Ltd | Method for producing diamond single crystal, diamond single crystal substrate, and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0492896A (en) * | 1990-08-09 | 1992-03-25 | Sumitomo Electric Ind Ltd | Vapor-phase synthesized diamond |
| JPH0717794A (en) * | 1993-06-30 | 1995-01-20 | Sumitomo Electric Ind Ltd | Diamond single crystal |
| JPH09165295A (en) * | 1994-12-05 | 1997-06-24 | Sumitomo Electric Ind Ltd | Diamond single crystal little in defect and synthetic method therefor |
| WO2001096633A1 (en) * | 2000-06-15 | 2001-12-20 | Element Six (Pty) Ltd | Single crystal diamond prepared by cvd |
| JP2003277183A (en) * | 2002-03-22 | 2003-10-02 | Sumitomo Electric Ind Ltd | Method for producing diamond single crystal, diamond single crystal substrate, and method for producing the same |
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